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    重庆时时彩注册需要啥: 五环化合物.pdf

    关 键 词:
    环化
      专利查询网所有资源均是用户自行上传分享,仅供网友学习交流,未经上传用户书面授权,请勿作他用。
    摘要
    申请专利号:

    CN96194915.5

    申请日:

    1996.04.25

    公开号:

    CN1188477A

    公开日:

    1998.07.22

    当前法律状态:

    终止

    有效性:

    无权

    法律详情: 未缴年费专利权终止IPC(主分类):C07D 493/08申请日:19960425授权公告日:20021127终止日期:20150425|||授权||||||公开
    IPC分类号: C07D493/08 主分类号: C07D493/08
    申请人: 第一制药株式会社;
    发明人: 寺沢弘文; 曾我恒彦; 石山崇
    地址: 日本东京中央区
    优先权: 1995.04.28 JP 106295/95
    专利代理机构: 中国专利代理(香港)有限公司 代理人: 张元忠;王其灏
    PDF完整版下载: PDF下载
    法律状态
    申请(专利)号:

    CN96194915.5

    授权公告号:

    |||1094940||||||

    法律状态公告日:

    2016.06.15|||2002.11.27|||1998.07.29|||1998.07.22

    法律状态类型:

    专利权的终止|||授权|||实质审查请求的生效|||公开

    摘要

    本发明涉及一种由式(Ⅰ)表示的具有抗肿瘤活性的新的紫杉酚衍生物。在式(Ⅰ)中,R1:苯基,R2:烷基、链烯基、炔基、环烷基或烷氧基,R3:氢原子、羟基、卤原子、烷氧基、-O-R31基团、酰氧基或-O-CO-R31基团[其中R31:烷基氨基、链烯基、炔基、环烷基、芳基或杂环基团],R4和R5:氢原子、烷基、链烯基、炔基、芳基或杂环基团,Z1:氢原子、羟基、卤原子或烷基,Z2:氢原子、羟基、卤原子或烷基,Z3:烷基、链烯基、炔基、环烷基、芳基或杂环基团。

    权利要求书

    1: 一种由下面通式(I)表示的化合物或其盐: 其中: R 1 表示苯基,它可具有一个或多个选自卤原子、烷基和烷氧基的取 代基; R 2 表示烷基、链烯基、炔基、环烷基或烷氧基,在这些烷基、链烯 基、炔基、环烷基和烷氧基中它们可具有一个或多个取代基,取代基选 自卤原子、羟基、羧基、烷氧基、芳氧基、苯基、氨基、烷基氨基、烷 氧基羰基、芳氧基羰基、?;?、酰氨基和酰氧基; R 3 表示氢原子、羟基、卤原子、烷氧基、-O-R 31 基团、酰氧基 或-O-CO-R 31 基团,其中的烷氧基和芳氧基可具有一个或多个取 代基,该取代基选自卤原子、羟基、羧基、环烷基、烷氧基、芳基、芳 氧基、氨基、烷基氨基、烷氧基羰基、芳氧基羰基、?;?、酰氨基、酰 氧基和杂环基团(该杂环基团可在其环的构成原子上具有一个或多个烷 基), 其中的R 31 表示烷基氨基、链烯基、炔基、环烷基、芳基或杂环基 团,其中的这些烷基氨基、链烯基、炔基、环烷基、芳基和杂环基团可 以具有一个或多个取代基,该取代基选自卤原子、羟基、羧基、烷基、 烷氧基、芳氧基、苯基、氨基、烷基氨基、氨基烷基、烷基氨基烷基、 烷氧基羰基、芳氧基羰基、?;?、酰氨基、酰氧基和具有3-8节环的 含氮杂环基团(该含氮杂环基团可在其环的构成原子上具有一个或多个 烷基), 或者R 3 可与甲基一起形成三节环,该甲基连接在与R 3 所连接的碳 原子相邻的碳原子上; R 4 和R 5 每个均表示氢原子、烷基、链烯基、炔基、芳基或杂环基 团,其中这些烷基、链烯基、炔基、芳基和杂环基团可以具有一个或多 个取代基,该取代基选自烷氧基、氨基、烷基氨基、氨基烷基、烷基氨 基烷基和由下式: 表示的5节或6节环的含氮饱和杂环基团,式中X表示氧原子、硫原子、 CH 2 、CH-Y、NH或N-Y,其中Y是烷基,(所述杂环基团在 构成其环的碳原子上可以具有一个或多个烷基), 或者R 4 和R 5 可与连于其上的碳原子一起形成硫代羰基或羰基; Z 1 表示氢原子、羟基、卤原子或烷基; Z 2 表示氢原子、羟基、卤原子或烷基; Z 3 表示烷基、链烯基、炔基、环烷基、芳基或杂环基团,其中的这 些烷基、链烯基、炔基、环烷基、芳基和杂环基团可以具有一个或多个 取代基,该取代基选自卤原子、羟基、羧基、烷基、烷氧基、苯基、氨 基、烷基氨基、氨基烷基、烷基氨基烷基、烷氧基羰基、芳氧基羰基、 ?;?、酰氨基和酰氧基;以及 Z 4 表示烷基、芳基或烷氧基,其中的这些烷基、芳基和烷氧基可具 有一个或多个取代基,该取代基选自卤原子、羟基、羧基、烷基、烷氧 基、苯基、氨基、烷基氨基、氨基烷基、烷基氨基烷基、烷氧基羰基、 芳氧基羰基、?;?、酰氨基和酰氧基; 条件是下面部分中的虚线意指该部分中的相应的键可以是双键,但在这 种情况下R 3 不是羟基。
    2: 权利要求1的化合物或其盐,其中的Z 1 和Z 2 是氟原子。
    3: 权利要求1的化合物或其盐,其中的Z 1 是羟基而Z 2 是氢原子。
    4: 权利要求1的化合物或其盐,其中的Z 1 是羟基而Z 2 是甲基。
    5: 权利要求1的化合物或其盐,其中的Z 4 是苯基。
    6: 权利要求1的化合物或其盐,其中的Z 4 是叔丁氧基。
    7: 权利要求1的化合物或其盐,其中的Z 3 是苯基。
    8: 权利要求1的化合物或其盐,其中的Z 3 是具有5节或6节环的 单环杂环基团。
    9: 权利要求1的化合物或其盐,其中的Z 3 是具有5节或6节环的 单环并含有一个氧、氮或硫原子作为环结构构成原子的杂环基团。
    10: 权利要求1的化合物或其盐,其中的Z 3 是具有5节或6节环的 单环并含有一个氧、氮或硫原子作为环结构构成原子的不饱和杂环基 团。
    11: 权利要求1的化合物或其盐,其中的Z 3 是呋喃基、吡咯基或吡 啶基。
    12: 权利要求1的化合物或其盐,其中的Z 3 是2-甲基-1-丙烯 基。
    13: 权利要求1的化合物或其盐,其中的R 2 是烷基。
    14: 权利要求1的化合物或其盐,其中的R 2 是甲基、乙基或丙基。
    15: 权利要求1的化合物或其盐,其中的R 2 是烷氧基。
    16: 权利要求1的化合物或其盐,其中的R 2 是甲氧基或乙氧基。
    17: 权利要求1的化合物或其盐,其中的R 2 是环烷基。
    18: 权利要求1的化合物或其盐,其中的R 2 是环丙基。
    19: 权利要求1的化合物或其盐,其中的R 4 或R 5 是烷基或氢原子。
    20: 权利要求1的化合物或其盐,其中的R 4 或R 5 是烷基、链烯基 或苯基,其中所述的烷基、链烯基或苯基可以具有一个或多个取代基, 该取代基选自羧基、烷氧基、芳氧基、烷氧基羰基、芳氧基羰基、氰基、 羟基、氨基、烷基氨基、?;?、酰氨基、酰氧基、烷氧基羰基氨基、烷 硫基、烷基亚磺?;?、烷基磺?;陀上率奖硎镜?节或6节环的含氮 饱和杂环基团: 式中X表示氧原子、硫原子、CH 2 、CH-Y、NH或N-Y,其中 Y表示烷基(所述杂环基团在构成其环的碳原子上可以具有一个或多个 烷基)。
    21: 权利要求20的化合物或其盐,其中所述的R 4 或R 5 的烷基、链 烯基或苯基的取代基是氨基、烷基氨基或由下列表示的5节或6节环的 含氮饱和杂环基团: 式中X表示氧原子、硫原子、CH 2 、CH-Y、NH或N-Y,其中 Y表示烷基(所述杂环基团在构成其环的碳原子上可以具有一个或多个 烷基)。
    22: 权利要求21的化合物或其盐,其中所述的5节或6节环的含氮 饱和杂环基团是由吗啉、硫代吗啉、哌嗪或4-烷基哌嗪衍生得到的。
    23: 权利要求1的化合物或其盐,其中的R 3 是羟基、氢原子或氟原 子。
    24: 权利要求1的化合物或其盐,其中的R 3 与甲基一起形成三节 环,该甲基连接在与R 3 所连接的碳原子相邻的碳原子上。
    25: 权利要求1的化合物,其中该化合物具有由下面通式(Ia)表 示的构型: 或其盐。

    说明书


    五环化合物

        【技术领域】

        本发明涉及一种新的具有抗肿瘤活性的紫杉酚衍生物。

        背景技术

        紫杉酚是具有下面化学结构的天然化合物,它可以从短叶红豆杉的树干等中少量地得到。

        已知紫杉酚具有抗肿瘤活性,其作用机理是基于在细胞分裂过程中微管的解聚抑制作用,因而希望作为不同于普通抗肿瘤剂的抗肿瘤剂而临床应用。

        尽管紫杉酚只能非常少量地从天然资源中获得,但目前已公开了关于合成紫杉酚衍生物的报道,在合成中使用由下面结构式表示的原料10-O-脱乙酰浆果赤霉素III:它是一种紫杉酚前体,可以从紫杉树的叶等中以相对大量地得到(参见JP-A-3-505725,本文所用“JP-A”指未审公开的日本专利申请)。这些衍生物中,由下面结构式表示的化合物(TaxotereTM)作为具有类似于或高于紫杉酚抗肿瘤活性的化合物已引起人们的注意,并且已经作为抗肿瘤剂而进行研究:

        尽管紫杉酚和TaxotereTM是所希望的抗肿瘤剂化合物,但其临床试验已证明它们对消化器官癌,特别是大肠癌的效果低,因而人们非常关心对具有更强抗肿瘤效果的衍生物的研究。

        本发明的内容

        紫杉酚衍生物的9位通常是酮基,但一些其中该位被还原的衍生物也是已知的。在9位具有α构型羟基的化合物已从天然资源中得到,已经报道了通过该化合物的化学改变而得到的各种9位α-羟基型衍生物(例如见医药化学杂志.,37,2655(1994))?;褂?,已知通过用还原剂还原10-O-脱乙酰浆果赤霉素III可化学合成在9位为β构型羟基地化合物,已经报道通过该化合物的化学改变可得到各种9位β-羟基型衍生物(例如见WO?94/20088)。

        作为深入研究的结果,本发明人发现当上述的9位β-羟基型紫杉酚衍生物中9位羟基和10位羟基被转化成环状缩醛型时其抗肿瘤活性急剧增加。本发明基于该发现而完成。

        因此,本发明涉及一种由下面通式(I)表示的化合物或其盐:其中:

        R1表示苯基,它可具有一个或多个选自卤原子、烷基和烷氧基的取代基;

        R2表示烷基、链烯基、炔基、环烷基或烷氧基,在这些烷基、链烯基、炔基、环烷基和烷氧基中它们可具有一个或多个取代基,取代基选自卤原子、羟基、羧基、烷氧基、芳氧基、苯基、氨基、烷基氨基、烷氧基羰基、芳氧基羰基、?;?、酰氨基和酰氧基;

        R3表示氢原子、羟基、卤原子、烷氧基、-O-R31基团、酰氧基或-O-CO′-R31基团,其中的烷氧基和芳氧基可具有一个或多个取代基,该取代基选自卤原子、羟基、羧基、环烷基、烷氧基、芳基、芳氧基、氨基、烷基氨基、烷氧基羰基、芳氧基羰基、?;?、酰氨基、酰氧基和杂环基团(该杂环基团可在其环的构成原子上具有一个或多个烷基),

        其中的R31表示烷基氨基、链烯基、炔基、环烷基、芳基或杂环基团,其中的这些烷基氨基、链烯基、炔基、环烷基、芳基和杂环基团可以具有一个或多个取代基,该取代基选自卤原子、羟基、羧基、烷基、烷氧基、芳氧基、苯基、氨基、烷基氨基、氨基烷基、烷基氨基烷基、烷氧基羰基、芳氧基羰基、?;?、酰氨基、酰氧基和具有3-8节环的含氮杂环基团(该含氮杂环基团可在其环的构成原子上具有一个或多个烷基),

        或者R3可与甲基一起形成三节环,该甲基连接在与R3所连接的碳原子相邻的碳原子上;

        R4和R5每个均表示氢原子、烷基、链烯基、炔基、芳基或杂环基团,其中这些烷基、链烯基、炔基、芳基和杂环基团可以具有一个或多个取代基,该取代基选自烷氧基、氨基、烷基氨基、氨基烷基、烷基氨基烷基和由下式:表示的5节或6节环的含氮饱和杂环基团,式中X表示氧原子、硫原子、CH2、CH-Y、NH或N-Y,其中Y是烷基,(所述杂环基团在构成其环的碳原子上可以具有一个或多个烷基),

        或者R4和R5可与连于其上的碳原子一起形成硫代羰基或羰基;

        Z1表示氢原子、羟基、卤原子或烷基;

        Z2表示氢原子、羟基、卤原子或烷基;

        Z3表示烷基、链烯基、炔基、环烷基、芳基或杂环基团,其中的这些烷基、链烯基、炔基、环烷基、芳基和杂环基团可以具有一个或多个取代基,该取代基选自卤原子、羟基、羧基、烷基、烷氧基、苯基、氨基、烷基氨基、氨基烷基、烷基氨基烷基、烷氧基羰基、芳氧基羰基、?;?、酰氨基和酰氧基;以及

        Z4表示烷基、芳基或烷氧基,其中的这些烷基、芳基和烷氧基可具有一个或多个取代基,该取代基选自卤原子、羟基、羧基、烷基、烷氧基、苯基、氨基、烷基氨基、氨基烷基、烷基氨基烷基、烷氧基羰基、芳氧基羰基、?;?、酰氨基和酰氧基;条件是下面部分中的虚线意指该部分中的相应的键可以是双键,但在这种情况下R3不是羟基。

        还有,本发明涉及具有由下面通式(Ia)表示的构型的化合物或其盐:其中的R1、R2、R3、R4、R5、Z1、Z2、Z3和Z4如上定义。

        首先,说明本文所用的术语。

        术语“C1-C6”意指1-6个碳原子,例如“C2-C6链烯基”指具有2-6个碳原子的链烯基。

        “烷基”、“链烯基”和“炔基”的每一个可以是直链或支链,优选具有1个碳原子(对于链烯基和炔基为2个碳原子)至6个碳原子。

        术语“烷氧基”指其中的烷基连接到-O-的基团,并且该烷基可被苯基(苯基可具有取代基)取代,如苄氧基、乙氧苯氧基、对甲氧基苄氧基等。优选的是该烷基部分具有1-6个碳原子。

        术语“烷氧基羰基”指其中的烷基连接在-COO-的氧原子上的基团,并且该烷基可被苯基(苯基可具有取代基)取代,如苄氧基羰基、乙氧苯氧基羰基、对甲氧基苄氧基羰基等。优选的是该烷基部分具有1-6个碳原子。

        术语“芳基”是指其中的一个氢原子从芳烃环上被去除后的一价基团,如苯基、甲苯基、联苯基、萘基等。

        在“氨基烷基”中,氨基可以键合在烷基的任一位置,并且该烷基优选具有1-6个碳原子。

        术语“烷基氨基”意指其中氨基被一个烷基所取代的基团,或者其中氨基被两个烷基取代的基团(这两个烷基彼此可以相同或不同)。该烷基部分优选具有1-6个碳原子。

        术语“?;币庵钙渲幸桓銮庠?、烷基或芳基连接在羰基(-CO-)上的基团,如甲?;?、乙?;?、丙?;?、苯甲?;?。在这种情况下,所连接的烷基优选具有1-6个碳原子,而苯基优选作为被连接的芳基。

        术语“杂环基团”意指具有一个或多个选自氧原子、氮原子和硫原子中至少一个原子的取代基团,并且是由单环或双环饱和的或不饱和的杂环化合物衍生得到,并且这些杂环基团可以在任何位置连接。单环杂环基团的例子包括由单环杂环化合物衍生得到的取代基,这些单环杂环化合物例如吡咯、呋喃、噻吩、吡咯烷、四氢呋喃、四氢噻吩、咪唑、吡唑、咪唑烷、吡唑烷、噁唑、噻唑、噁二唑、噻二唑、吡啶、二氢吡啶、四氢吡喃、哌啶、哒嗪、嘧啶、吡嗪、哌嗪、二噁烷、吡喃、吗啉等。双环杂环基团的例子包括由双环杂环化合物衍生得到的取代基,这些双环杂环化合物例如苯并呋喃、中氮茚、苯并噻吩、吲哚、1,5-二氮杂萘、喹喔啉、喹唑啉、苯并二氢吡喃等。

        术语“含氮杂环基团”意指由饱和或不饱和杂环化合物衍生得到的取代基,该杂环化合物总是具有一个氮原子作为杂环的构成原子,并且也可具有一个或多个选自氧原子、氮原子和硫原子的原子作为其它的构成原子。这种基团的例子包括吡咯、吡咯烷、咪唑、吡唑、咪唑烷、吡唑烷、噁唑、噻唑、噁二唑、噻二唑、吡啶、二氢吡啶、哌啶、哒嗪、嘧啶、吡嗪、哌嗪、吗啉、硫代吗啉等。

        “由下式表示的具有5或6节环的含氮饱和杂环基团,式中X代表氧原子、硫原子、CH2、CH-Y、NH或N-Y,其中Y是烷基,(该杂环基团在构成其环的碳原子上可以具有一个或多个烷基)“意指由饱和的杂环化合物衍生得到的取代基,该饱和的杂环化合物总是具有一个氮原子作为该杂环基团的构成原子并具有5节或6节环,其例子包括吡咯烷、咪唑烷、吡唑烷、噁唑烷、噻唑烷、异噁唑烷、异噻唑烷、哌啶、哌嗪、吗啉、硫代吗啉等。

        术语“R3可与甲基一起形成三节环,该甲基连接在与R3所连接的碳原子相邻的碳原子上”意指7位或8位部分形成下述的结构。

        下面,说明通式(I)中的每个取代基。

        作为R1的苯基的取代基的“烷基”和“烷氧基”的优选例子是具有1-3个碳原子的那些。

        R1的苯基的取代基数优选是1或2,并且该取代基优选在间位取代。

        未被取代的苯基优选作为R1?;褂叛〉氖蔷哂?或2个在间位取代的氟原子、氯原子、甲基或甲氧基的苯基。

        作为R2,优选烷基、烷氧基和环烷基。

        作为R2的“烷基”,优选C1-C6烷基,特别优选甲基、乙基和丙基。

        作为R2的“烷氧基”,优选C1-C6烷氧基,特别优选的是甲氧基和乙氧基。

        作为R2的“环烷基”,优选C3-C6环烷基,特别优选环丙基。

        作为R2,特别优选甲基、乙基、丙基、甲氧基、乙氧基或环丙基。

        作为R3的“卤原子”,优选氟原子。

        作为R3,特别优选的是氢原子、氟原子或羟基?;褂?,作为R3优选的是其中与甲基一起形成三节环的基团,该甲基连接在与R3所连接的碳原子(7位)相邻的碳原子(8位)上,即其中的7位和8位部分具有下述结构的基团。

        作为R4和R5的烷基,优选具有1-6个碳原子的那些,特别优选的是甲基、乙基和丙基。

        作为R4和R5的链烯基,优选具有2-6个碳原子的那些,特别优选的是烯丙基。

        作为R4和R5的烷基,链烯基或苯基的取代基,优选的是氨基、烷基氨基或由下式:表示的具有5节或6节环的含氮饱和的杂环基团,式中X表示氧原子、硫原子、CH2、CH-Y、NH或N-Y,其中Y是烷基,(该杂环基团在构成其环的碳原子上可以具有一个或多个烷基)。

        该烷基氨基中的烷基部分优选具有C1-C3烷基,并可以是二烷基取代(在二烷基取代的情况下,这两个烷基彼此可以相同或不同)。

        作为由下式表示的具有5节或6节环的含氮饱和的杂环基团(该杂环基团在构成其环的碳原子上可以具有一个或多个烷基),特别优选的是由哌嗪、吗啉、硫代吗啉、4-C1-C3烷基哌嗪衍生得到的基团。

        还有,作为在构成杂环基团环的碳原子上所取代的烷基,优选是甲基。

        作为R4和R5的优选例子是其中一个是氢原子或烷基而另一个是烷基、链烯基或苯基的组合。

        作为Z1和Z2的“卤原子”,优选是氟原子、氯原子和溴原子。

        作为Z1和Z2的“烷基”,优选是甲基、乙基和丙基。

        作为Z1,优选卤原子和羟基,而氟是特别优选的卤原子。

        作为Z2,优选卤原子、氢原子或烷基,其中作为卤原子特别优选氟原子,而作为烷基特别优选甲基。

        最优选的Z1和Z2的例子包括其中Z1是氟原子而Z2是氟原子的组合,其中Z1是羟基而Z2是氢原子的组合以及其中Z1是羟基而Z2是甲基的组合。

        作为Z3,优选芳基、杂环基团和链烯基。

        作为Z3的“芳基”,优选苯基。

        作为Z3的“链烯基”,优选2-甲基-1-丙烯基。

        作为Z3的杂环基团,优选单环杂环基团,更优选的是5节或6节环的单环杂环基团,例如吡咯、呋喃、噻吩、吡咯烷、四氢呋喃、四氢噻吩、咪唑、吡唑、咪唑烷、吡唑烷、噁唑、噻唑、噁二唑、噻二唑、吡啶、二氢吡啶、四氢吡喃、哌啶、哒嗪、嘧啶、吡嗪、哌嗪、二噁烷、吡喃、吗啉等。

        在Z3的杂环基团中,更优选的是具有一个氧原子、氮原子或硫原子作为环结构的构成原子的5节或6节环单环杂环基团,这种基团的例子包括由吡咯、呋喃、噻吩、吡咯烷、四氢呋喃、四氢噻吩、吡啶、二氢吡啶、四氢吡喃、哌啶、吡喃等衍生得到的那些基团。

        在Z3的杂环基团中,最优选的是具有一个氧原子、氮原子或硫原子作为环结构的构成原子的5节或6节环单环不饱和杂环基团,这种基团的例子包括由呋喃、吡啶和吡咯衍生得到的那些基团。

        作为Z3,特别优选的是2-甲基-1-丙烯基、苯基、呋喃基、吡啶基和吡咯基。

        作为Z4,优选芳基或烷氧基。

        作为Z4的“芳基”,优选苯基。

        作为Z4的“烷氧基”,优选叔丁氧基。

        作为Z4,特别优选的是苯基和叔丁氧基。

        优选地,本发明的化合物可具有下列构型。

        取代基Z3所连接的3′-位的构型可以是两种构型中的任一种,但优选是天然紫杉酚相同的构型?;褂?,7-位的构型或者是α-或者是β-构型。

        本发明的紫杉酚衍生物可以是游离形式和酸式加成盐或羧酸盐的形式。酸式加成盐的例子包括无机酸盐如盐酸盐、硫酸盐、硝酸盐、氢溴酸盐、氢碘酸盐、磷酸盐等和有机酸盐如乙酸盐、甲磺酸盐、苯磺酸盐、甲苯磺酸盐、柠檬酸盐、马来酸盐、富马酸盐、乳酸盐等。

        羧基的盐的例子可以是无机盐或是有机盐,这包括碱金属盐如锂盐、钠盐、钾盐等,碱土金属盐如镁盐、钙盐等,以及铵盐、三乙胺盐、N-甲基葡糖胺盐、三-(羟甲基)氨基甲烷盐等。

        下面说明本发明化合物的制造方法。在进行反应中,如果需要取代基可以用?;せ沤斜;?,并且每个取代基团的转化顺序没有特别限制。

        在上述反应图解中,R13意指R3自身或用?;せ疟;さ腞3(当R3被羟基、氨基等取代或当R3是羟基时);

        R14意指R4自身或用?;せ疟;さ腞4(当R4被氨基等取代时);

        R15意指R5自身或用?;せ疟;さ腞5(当R5被氨基等取代时);

        Z11意指Z1自身或用?;せ疟;さ腪1(当Z1是羟基时);

        Z21意指Z2自身或用?;せ疟;さ腪2(当Z2是羟基时);

        Z31意指Z3自身或用?;せ疟;さ腪3(当Z3被羟基、氨基等取代时);以及

        Z41意指Z4自身或用?;せ疟;さ腪4(当Z4被羟基、氨基等取代时)。

        R8和R9独立地是氢原子、烷基、芳基等,在优选的组合中,两者均是甲基,或者一个是对甲氧基苯基而另一个是氢原子。

        R10和R11是羟基的?;せ?。

        通过在酸性催化剂如10-樟脑磺酸、对甲苯磺酸等存在下,将由10-O-脱乙酰浆果赤霉素III〔化合物(1)与由R14C(=O)R15表示的醛或酮或者由R14R15C(OR45)2(R45是甲基或类似的烷基)表示的缩醛反应〕衍生的化合物(2)而得到化合物(3)。接着,通过按已报道的相应的普通方法将化合物(3)的13位羟基与化合物(A)、(B)或(C)缩合而得到化合物(4)。

        作为与化合物(A)或(B)的缩合反应,已知的方法是在4-二甲基氨基吡啶或类似碱性催化剂存在下使用羧酸活化剂如碳酸二(2-吡啶基)酯或二环己基碳化二亚胺。在此缩合反应中,当使用化合物(A)时,Z11和Z21变成氢原子和羟基的组合。

        作为与化合物(C)的缩合反应,已知的方法是使用六甲基二硅杂叠氮化钠或类似的碱。

        在这一反应步骤中,化合物(A)、(B)或(C)某些情况下会与化合物(3)的7位羟基反应。在这种情况下,用硅胶柱色谱法或类似方法可将感兴趣的产物分离和纯化。另外,由于通过选择合适的?;せ藕头从μ跫傻玫狡渲薪;せ叛≡裥缘匾氲交衔?3)7位的化合物(5)(特别是在甲氨酸酯型?;せ徘榭鱿驴傻玫礁哐≡裥?,例如通过于0℃在吡啶中与2,2,2-三氯乙氧基碳酰氯进行反应而用2,2,2-三氯乙氧基羰基基团选择性地?;?位),化合物(4)可以通过与上述相同的方式将化合物(5)和13位羟基与化合物(A)、(B)或(C)缩合而合成?;衔?5)也可通过另一方法得到,其中用二氧化锰或类似氧化剂将化合物(3)的13位羟基转化为酮,将?;せ乓胨没衔锏?位羟基以得到化合物(6),随后用氢硼化钠或类似还原剂将13位的酮再还原成羟基。

        在需要时,在由此得到的化合物(4)的每个取代基转化或去?;ぶ?,通过分别将2位苯甲?;蒀OR1、将4位乙?;蒀OR2、将7位羟基转化为R3、以及R14、R15、Z11、Z21、Z31和Z41分别转化成R4、R5、Z1、Z2、Z3和Z4而得到感兴趣的化合物(I)。这种转化和去?;た梢杂糜谢У耐ǔ<际踅?,例如下面的例子。

        例如,按照文献(四面体通迅,35,8931(1994))中所述方法可实现将2位苯甲?;蒀OR1,其中2位的酯键被选择性地水解,然后乙?;?,由此可得到R1不是苯基的化合物。

        例如,按照下述方法可实现将4位乙?;蒀OR2,该方法中于-100℃至室温的温度下在存有六甲基二硅杂叠氮化钠或类似碱下进行与由R21-X表示的化合物的反应(式中R21表示烷基、链烯基或芳基,而X表示卤原子如碘原子、溴原子等或离子基团如甲磺?;?、对甲苯磺?;?,由此得R2不是甲基的化合物。

        其中的R2不是甲基的化合物也可以通过下述方法得到,即在存有六甲基二硅杂叠氮化钠或类似碱下将化合物(6)与由R21-X表示的化合物反应则得到其中该4位乙?;蛔蒀OR2的化合物,随后还原13位羟基并且最后进行与化合物(A)、(B)或(C)的缩合反应。

        通过各种依赖于R3类型的方法可实现将7位羟基转化成R3。用已知方法(例如见有机化学杂志,58,5028(1993))通过去除7位羟基可得到其中R3是氢的化合物。其中R3是-OC(=O)R31的化合物可以通过有机化学的一般技术用羧酸或酸性氯化物将7位羟基乙?;玫?。其中R3是-OC(=O)NQ1Q2(Q1和Q2独立地是氢原子或烷基)的化合物可以通过下述方法得到,在该方法中,将7位羟基与由ClC(=O)OR32(R32是对硝基苯基或类似的芳基)表示的化合物反应,然后再与胺反应;将7位羟基在存有胺下与光气反应;将7位羟基与由ClC(=O)NQ1Q2(Q1和Q2独立地是氢原子或烷基)表示的化合物反应或者将7位羟基与由R31N=C=O表示的异氰酸酯反应。转化成感兴趣的R3也可以通过将7位羟基转化然后进行几步有机化学转化而实现。

        在另一种方法中,通过用不同于?;せ臨10的?;せ臨11?;せ衔?5)的13位羟基、去除R10以得到化合物(8)、按上述相同方式将化合物(8)的7位羟基转化成R13并且然后去除?;せ臨11而得到化合物(9)。之后,化合物(9)的13位羟基与化合物(A)、(B)或(C)缩合、并且然后进行各种取代基团的转化和去?;ぴ虻玫礁行巳さ幕衔?I)。关于此,化合物(8)可以通过选择合适的?;せ臨11和反应条件而直接由化合物(3)合成,而化合物(9)也可通过转化7位羟基而直接由化合物(3)合成。

        通过在四氢呋喃、二氯甲烷、乙醚、甲苯、1,1-二甲氧基乙烷或它们的混合溶剂中用三氟化二乙氨基硫处理具有7位羟基的化合物,可以得到其中R3是卤原子的感兴趣的化合物,例如其中R3是氟原子的化合物。

        化合物(8)也可由化合物(D)合成,该化合物(D)是由化合物(1)得到的。即,用不同于2,2,2-三氯乙氧基羰基基团的?;せ;せ衔?D)的13位羟基,去除7位和10位的2,2,2-三氯乙氧基羰基,然后用还原剂如氢硼化叔丁铵等处理由此得到的化合物以将9位酮转化成羟基并以上述相同的方式使其与醛、酮或缩醛反应,由此得到化合物(8)。

        作为生产料的下述化合物由已报道的方法合成。

        化合物(2):WO?94/20088及其它方法。

        化合物(D):四面体,42,4451(1986)和其它方法。

        化合物(A):四面体通迅,33,5185(1992)和其它方法。

        化合物(B):美国化学学会杂志,110,5917(1988)和其它方法。

        化合物(C):四面体通迅,34,4149(1993)和其它方法。

        在上述合成方法中,通常得到其中7位具有β构型的化合物。因为已经知道当用碱处理其中的9位是酮基而7位未被?;さ淖仙挤友苌锸?,7位的羟基的构型由β构型异构体α构型,因此可以通过在异构化后将9位酮基还原成羟基而合成在7位具有α构型的化合物。

        本发明的化合物可用于治疗各种癌症如肺癌、消化器官癌、卵巢癌、子宫癌、乳房癌、肝癌、头和颈癌、血癌、肾癌、睾丸癌等。

        本发明的化合物可以以静脉、肌内、皮下等各种注射给药或者通过其它各种途径给药如口服给药、经皮吸收等。在这些方法中,用溶液的静脉注射和口服给药是所希望的。该溶液可以通过与药物可接受的酸或钠等碱金属盐形成酸式加成物而制备。对于口服给药的情况,该化合物可以是其游离形式或盐形式。

        合适的药物制剂按照相应的每种给药方法来选择并用常用制备方法来制造。本发明抗肿瘤剂的剂型中,口服制剂的例子包括片剂、粉剂、粒剂、胶囊、溶液、糖浆、酏剂、油剂或水液悬乳剂等。对于注射液,在制剂中可使用稳定剂、抗茵剂、加溶剂等。含有这些辅剂的注射液可被配制在容器中并有冻干或类似方法制成固体制剂,在使用之前再溶解。

        液体制剂包括溶液、悬浮液、乳液等,当制备这些制剂时可使用悬浮剂,乳化剂等作为添加剂。

        本发明的化合物可用于治疗哺乳动物的癌,特别是人体中的癌。对于人类来说,优选地是一天中以合适的间隔重复服药一次。

        给药的剂量为每1m2体表面积服药约0.5-50mg,优选约1-20mg。实现本发明的最佳方式

        现在通过参考例和实施例更详细地说明本发明,但应理解的是本发明并不限于此。本发明实施例1步骤1:9β-10-脱乙?;?9-二氢浆果赤霉素III

        将6.98克10-脱乙酰浆果赤霉素III溶于由200ml无水二氯甲烷和200ml无水1,4-二噁烷组成的混合溶液中,于室温将12.89克的氢硼化叔丁基铵加到所得溶液中并于相同温度下搅拌19小时。将该反应溶液冷却至0℃并逐滴加入1N盐酸将其中和。在减压下浓缩该溶液以蒸发大部分的有机溶剂。将所得残余物与乙酸乙酯和水混合并摇动以分离有机层,并用乙酸乙酯萃取水层。用饱和盐水洗涤整个有机层并经无水硫酸钠干燥。之后,在减压下蒸发溶剂,用硅胶柱色谱法纯化所得残余物(展开溶剂:氯仿∶丙酮=5∶1(v/v))则得到4.794克的呈白色固体的标题化合物。Rf=0.65(氯仿∶甲醇=7∶1(v/v))FAB质谱:546(M+)。步骤2:9β-10-脱乙?;?9-二氢-9,10-O-异亚丙基浆果赤霉素III

        将0.4825克的上述步骤1中所得化合物溶于4.8ml无水二氯甲烷和4.8ml无水1,4-二噁烷中,于室温向所得溶液中加入0.54ml?2,2-二甲氧基丙烷和19.9mg樟脑磺酸,并静置1小时。将溶液冷却至0℃并加入三乙胺调至pH7,然后在减压下蒸发溶剂。之后,用硅胶柱色谱法(展开溶剂:氯仿∶丙酮=5∶1(v/v))纯化所得的残余物,则得到0.2949克呈白色固体的标题化合物。Rf=0.36(氯仿∶丙酮=6∶1(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.16(3H,s),1.41(3H,s),1.57(3H,s),1.63(3H,

        ???s),1.64(3H,8),1.70-2.20(4H,m),3.04(1H,d,

        ???J=4.9Hz),3.85(1H,d,J=7.3Hz),4.04(1H,br-d),

        ???4.33(1H,d,J=8.3Hz),4.39(1H,d,J=8.3Hz),

        ???4.67(1H,d,J=7.8Hz),4.80(1H,br),5.06(1H,s),

        ???5.58(1H,d,J=7.3Hz),6.02(1H,d,J=4.9Hz),

        ???7.49(2H,t,J=7.3Hz),7.59(1H,t,J=7.3Hz),

        ???8.13(2H,d,J=7.3Hz).步骤3:9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-(三异丙基甲硅烷氧基)丙?;?10-脱乙?;?9-二氢-9,10-O-异亚丙基浆果赤霉素III

        于-58℃将49.8mg上述步骤2得到的化合物和49.0mg(3R,4R)-1-(叔丁氧基羰基)-4-(2-呋喃基)-3-(三异丙基甲硅烷氧基)氮杂环丁-2-酮溶解在3.4ml无水四氢呋喃中,随后滴加1N六甲基二硅杂叠氮化钠(四氢呋喃溶液)。30分钟之后,于-50℃将所得溶液与饱和氯化铵水溶液混合,并用乙酸乙酯萃取。用饱和盐水洗涤该萃取液并经无水硫酸钠干燥。之后,在减压下蒸发溶剂并用硅胶薄层色谱法(展开溶剂:己烷∶乙酸乙酯=4∶1(v/v))纯化所得的残余物,则得到15.6mg呈无色透明浆状的标题化合物。Rf=0.09(己烷∶乙酸乙酯=4∶1(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.91-1.02(22H,m),1.06(3H,s),1.30(3H,s),

        ???1.39(9H,s),1.58(3H,s),1.67(3H,s),1.68(3H,

        ???s),1.76(3H,s),1.87(1H,br-s),2.15-2.23(2H,

        ???m),2.26-2.39(2H,m),2.45(3H,s),2.97(1H,d,

        ???J=4.9Hz),3.89(1H,d,J=7.3Hz),4.01-4.09

        ???(1H,m),4.31(1H,d,J=8.3Hz),4.39(1H,d,J=

        ???8.3Hz),4.68(1H,br-d,J=6.8Hz),4.99(1H,s),

        ???5.12(1H,s),5.23-534(2H,m),5.53(1H,d,J=

        ???7.3Hz),6.02(1H,d,J=4.9Hz),6.10(1H,br-t,J=

        ???8.0Hz),6.25(1H,J=3.4Hz),6.34(1H,dd,J=

        ???3.4Hz,1.9Hz),7.37(1H,d,J=1.9Hz),7.48(2H,t,

        ???J=7.3Hz),7.59(1H,t,J=7.3Hz),8.12(2H,d,J=

        ???7.3Hz).步骤4:9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?10-脱乙?;?9-二氢-9,10-O-异亚丙基浆果赤霉素III

        将44.3mg上述步骤3中得到的化合物溶于2.21ml无水吡啶中,于0℃将该溶液与0.44ml氟化氢-吡啶混合,再回到室温然后搅拌14小时。将所得溶液于冷至0℃的水混合,随后用乙酸乙酯萃取。依次用1N盐酸、饱和碳酸氢钠水溶液和饱和盐水洗涤该有机层,并经无水硫酸钠干燥。之后,在减压下蒸发溶剂并用硅胶薄层色谱法(展开溶剂:氯仿∶丙酮=6∶1(v/v))纯化所得残余物,则得到33.9mg呈无色透明浆状的标题化合物。Rf=0.32(氯仿∶丙酮=6∶1(v/v))熔点:132-135℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.08(3H,s),1.28(3H,s),1.41(9H,s),1.58(3H,

        ???s),1.65(3H,s),1.67(3H,s),1.70(3H,s),1.83-

        ???1.94(1H,m),2.07-2.27(2H,m),2.36(3H,s),

        ???2.29-2.47(1H,m),2.94(1H,d,J=4.9Hz),3.83

        ???(1H,d,J=7.3Hz),4.32(1H,d,J=8.7Hz),4.39

        ???(1H,d,J=8.7Hz),4.65-4.76(2H,m),5.10(1H,

        ???s),5.30-5.42(2H,m),5.54(1H,d,J=7.3Hz),

        ???6.05(1H,d,J=4.9Hz),6.11(1H,d,J=3.5Hz),

        ???6.36(1H,dd,J=3.5Hz,1.4Hz),7.39(1H,d,J=

        ???1.4Hz),7.48(2H,t,J=7.3Hz),7.60(1H,t,J=

        ???7.3Hz),8.11(2H,d,J=7.3Hz).FAB质谱:840(MH+)。本发明实施例2步骤1:9β-10-脱乙?;?9-二氢-9,10-O-(4-甲氧基亚苄基)浆果赤霉素III

        将本发明实施例1的步骤1中得到的化合物进行与本发明实施例1的步骤2相同的反应,不同之处是用4-甲氧基苯甲醛缩二甲醇代替2,2-二甲氧基丙烷,由此得到呈无色透明浆状的标题化合物。Rf=0.24(氯仿∶丙酮=10∶1(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.19(3H,s),1.50(3H,s),1.61(3H,s),1.98(3H,

        ???s),1.96-2.43(m),2.34(3H,s),3.10(1H,d,J=

        ???4.9Hz),3.84(3H,s),3.98(1H,d,J=7.3Hz),4.09-

        ???4.19(1H,m),4.31(1H,d,J=8.3Hz),4.39(1H,d,

        ???J=8.3Hz),4.57(1H,d,J=7.8Hz),4.84(1H,q,J=

        ???7.2Hz),5.07(1H,s),5.47(1H,d,J=7.3Hz),5.80

        ???(1H,s),6.04(1H,d,J=4.9Hz),6.93(2H,d,J=

        ???8.8Hz),7.42-7.55(4H,m),7.60(1H,t,J=7.4Hz),

        ???8.12(2H,d,J=7.4Hz).步骤2:9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-(三异丙基甲硅烷氧基)丙?;?10-脱乙?;?9-二氢-9,10-O-(4-甲氧基亚苄基)浆果赤霉素III

        使用上述步骤1所得化合物作原料,按本发明实施例1的步骤3中所述相同方式进行该原料与(3R,4R)-1-(叔丁氧基羰基)-4-(2-呋喃基)-3-(三异丙基甲硅烷氧基)氮杂环丁-2-酮的反应,由此得到呈无色透明浆状的标题化合物。Rf=0.28(己烷∶乙酸乙酯=5∶2(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.91-1.08(21H,m),1.32(3H,s),1.54(3H,s),

        ???1.72(3H,s),1.80(3H,s),1.40(9H,s),2.17-2.28

        ???(2H,m),2.36(2H,d,J=8.2Hz),2.47(3H,s),3.02

        ???(1H,d,J=5.0Hz),3.84(3H,s),4.00(1H,d,J=

        ???7.8Hz),4.07-4.16(1H,m),4.29(1H,AB?type?d,J=

        ???8.2Hz),4.39(1H,AB?type?d,J=8.2Hz),4.61(1H,d,

        ???J=7.8Hz),5.00(1H,s),5.12(1H,s),5.22-5.36

        ???(2H,m),5.41(1H,d,J=7.8Hz),5.76(1H,s),6.05

        ???(1H,d,J=5.0Hz),6.11(1H,br-t,J=8.2Hz),6.26

        ???(1H,d,J=3.6Hz),6.34(1H,dd,J=3.6Hz,2.0Hz),

        ???6.93(2H,d,J=8.8Hz),7.38(1H,d,J=2.0Hz),

        ???7.43-7.53(4H,m),7.59(1H,t,J=7.9Hz),8.02

        ???(2H,d,J=7.9Hz).步骤3:9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?10-脱乙?;?9-二氢-9,10-O-(4-甲氧基亚苄基)浆果赤霉素III

        使用上述步骤2所得化合物作原料,重复本发明实施例1步骤4的反应过程,则得到呈无色透明浆状的标题化合物。Rf=0.15(氯仿∶丙酮=7∶1(v/v))熔点:148-151℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.30(3H,s),1.42(9H,s),1.56(3H,s),1.76(6H,

        ???s),2.10-2.26(3H,m),2.36(3H,s),2.31-2.48

        ???(1H,m),2.99(1H,d,J=4.9Hz),3.84(3H,s),3.98

        ???(1H,d,J=7.4Hz),4.06-4.17(1H,m),4.30(1H,AB

        ???type?d,J=8.3Hz),4.38(1H,AB?type?d,J=8.3Hz),

        ???4.57(1H,d,J=8.3Hz),4.72(1H,d,J=3.9Hz),

        ???5.11(1H,s),5.38(2H,br-s),5.43(1H,d,J=

        ???7.4Hz),5.80(1H,s),6.07(1H,d,J=4.9Hz),6.15

        ???(1H,br-t,J=8.0Hz),6.32(1H,d,J=3.8Hz),

        ???6.36(1H,dd,J=3.8Hz,2.0Hz),6.93(2H,d,J=

        ???8.8Hz),7.40(1H,d,J=2.0Hz),7.43-7.53(4H,m),

        ???7.60(1H,t,J=7.3Hz),8.11(2H,d,J=7.3Hz).FAB质谱:918(M+)。本发明实施例3步骤1:9β-13-O-烯丙氧基羰基-10-脱乙?;?9-二氢-9,10-O-异亚丙基浆果赤霉素III

        将98.6mg本发明实施例1的步骤2中得到的化合物溶于4.0ml四氢呋喃中,于-78℃将1.64N正丁基锂(己烷溶液,0.31ml)滴加至所得溶液中,五分钟之后向其中加入0.025ml烯丙氧基碳酰氯。30分钟后,将所得溶液与饱和氯化铵水液混合并用乙酸乙酯萃取。用饱和盐水洗涤该有机层并经无水硫酸钠干燥。之后,在减压下蒸发溶剂并用硅胶柱色谱法(展开溶剂:己烷∶乙酸乙酯=5∶4(v/v))纯化所得残余物,则得到52.8mg的呈无色透明浆状的标题化合物。Rf=0.39(己烷∶乙酸乙酯=5∶4(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.23(3H,s),1.40(3H,s),1.58(3H,s),1.64(3H,

        ???s),1.65(3H,s),1.80(3H,s),2.11-2.27(2H,m),

        ???2.26-2.38(2H,m),2.31(3H,s),2.98(1H,d,J=

        ???4.8Hz),3.90(1H,d,J=7.8Hz),4.01-4.09(1H,m),

        ???4.26(1H,AB?type?d,J=8.3Hz),4.39(1H,AB?type?d,

        ???J=8.3Hz),4.56(1H,d,J=6.8Hz),4.63-4.76(2H,

        ???m),5.11(1H,m),5.28-5.44(2H,m),5.56(1H,d,

        ???J=7.3Hz),5.85-6.05(1H,m),6.00(1H,d,J=

        ???4.8Hz),7.47(2H,t,J=7.8Hz),7.59(1H,t,J=

        ???7.8Hz),8.11(2H,d,J=7.8Hz).步骤2:9β-13-O-烯丙氧基羰基-10-脱乙?;?9-二氢-9,10-O-异亚丙基-7-O-三乙基甲硅烷基浆果赤霉素III

        于室温52.8mg上述步骤1得到的化合物溶于2.2ml的无水二氯甲烷中,随后向其中加入0.036ml的2,6-卢剔啶。冷至-40℃后,向其中滴加0.062ml三氟甲磺酸三乙基甲硅烷酯,随后搅拌25分钟。将所得溶液于-40℃下与饱和碳酸氢钠水液混合并用氯仿萃取。用饱和盐水洗涤该有机层并经无水硫酸钠干燥。之后在减压下蒸发溶剂并用硅胶柱色谱法纯化所得残余物(展开溶剂∶己烷∶乙酸乙酯=4∶1(v/v))则得到34.1mg的呈无色透明浆状的标题化合物。Rf=0.32(己烷∶乙酸乙酯=3∶1(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.56-0.71(6H,m),1.15(3H,s),1.39(3H,s),1.47

        ???(3H,s),1.51(3H,s),1.58(3H,s),1.81(3H,s),

        ???2.05-2.15(1H,m),2.20-2.34(2H,m),2.30(3H,

        ???s),2.39(1H,dd,J=7.6Hz,14.0Hz),3.22(1H,d,

        ???J=5.8Hz),3.95(1H,dd,J=3.4Hz,9.8Hz),4.28

        ???(1H,AB?type?d,J=7.8Hz),4.47(1H,AB?type?d,J=

        ???7.8Hz),4.56(1H,br-d,J=9.3Hz),4.68(2H,d,J=

        ???5.9Hz),4.82(1H,t,J=7.2Hz),5.27-5.33(1H,m),

        ???5.34-5.41(1H,m),5.43(1H,d,J=9.3Hz),5.82-

        ???6.01(1H,m),5.86(1H,d,J=7.8Hz),5.88(1H,t,

        ???J=7.6Hz),7.47(2H,t,J=7.8Hz),7.58(1H,t,J=

        ???7.8Hz),8.09(2H,d,J=7.8Hz).步骤3:9β-10-脱乙?;?9-二氢-9,10-O-异亚丙基-7-O-三乙基甲硅烷基浆果赤霉素III

        在氮气氛下将32.1mg上述步骤2所得化合物溶解于1.0ml四氢呋喃中,并将该溶液与0.005ml甲醇和4.3mg四三苯膦钯混合并搅拌1小时。之后,在减压下蒸发溶剂并用硅胶薄层色谱法(展开溶剂:己烷∶乙酸乙酯=5∶3(v/v))纯化所得残余物,则得到17.1mg呈无色透明浆状的标题化合物。Rf=0.29(己烷∶乙酸乙酯=5∶3(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.61(6H,q,J=7.8Hz),0.96(9H,t,J=7.8Hz),

        ???1.11(3H,s),1.40(3E,s),1.50(3H,s),1.57(3H,

        ???s),1.59(3H,s),1.93(3H,s),1.88-2.15(2H,m),

        ???2.23-2.47(2H,m),232(3H,s),3.16(1H,d,J=

        ???5.3Hz),4.17(1H,t,J=4.8Hz),4.17-4.29(1H,m),

        ???4.20(1H,AB?type?d,J=7.8Hz),4.29(1H,AB?type?d,

        ???J=7.8Hz),4.73-4.88(2H,m),5.51(1H,d,J=

        ???7.8Hz),5.91(1H,d,J=5.3Hz),7.48(2H,t,J=

        ???7.3Hz),7.59(1H,t,J=7.3Hz),8.14(2H,d,J=

        ???7.3Hz).步骤4:9β-13-O-〔3-(叔丁氧基羰基氨基)-2-(叔丁基二甲基甲硅烷氧基)-3-(4-吡啶基)丙?;?10-脱乙?;?9-二氢-9,10-O-异亚丙基-7-O-三乙基甲硅烷基浆果赤霉素III

        使用上述步骤3中得到的化合物作原料,按照本发明实施例1步骤3所述相同方式进行该原料与顺-1-(叔丁氧羰基)-3-(叔丁基二甲基甲硅烷氧基)-4-(4-吡啶基)氮杂环丁-2-酮的反应,则得到呈无色透明浆状的标题化合物,该化合物是两种非对映体的混合物,其中2′-位和3′-位的相对构型是苏(顺式)型。Rf=0.32(己烷∶乙酸乙酯=5∶4(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???-0.30-0.37(m),0.60-1.02(m),1.25-1.88(m),

        ???2.10-2.58(m),2.24?and?2.54(total?3H,each?s),

        ???3.10?and?3.15(total?1H,each?d,J=5.4Hz,J=

        ???5.9Hz),3.92-4.18(m),4.21-4.60(m),4.84?and

        ???4.94(total?1H,each?t,J=6.3Hz,J=4.8Hz),5.21-

        ???5.68(m),5.88?and?5.94(total?1H,each?d,J=5.9Hz,

        ???J=5.4Hz),6.18-6.30(m),7.18-7.64(m),8.11

        ???(2H,d,J=7.3Hz),8.52-8.70(m).步骤5:9β-13-O-〔3-(叔丁氧基羰基氨基)-2-羟基-3-(4-吡啶基)丙?;?10-脱乙?;?9-二氢-9,10-O-异亚丙基浆果赤霉素III

        于0℃下将27.1mg上述步骤4所得的化合物溶于1.35ml吡啶中,随后向其中滴加0.27ml氟化氢-吡啶,之后在室温下搅拌6小时。在加入冷至0℃的水后,用乙酸乙酯萃取所得溶液。用饱和盐水洗涤该有机层并经无水硫酸钠干燥。之后,在减压下蒸发溶剂并用硅胶薄层色谱法纯化所得残余物(展开溶剂:氯仿∶甲醇=12∶1(v/v)),则得到标题化合物的两种非对映体中的低极性异构体A和高极性异构体B,其中2′-位和3′-位的相对构型是苏(顺式)型,这两种异构体的每一种均呈无色透明浆状。异构体ARf=0.27(氯仿∶甲醇=12∶1(v/v))熔点:157-159℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.24(3H,s),1.40(3H,s),1.51(3H,s),1.58(3H,

        ???s),1.63(3H,s),1.66(3H,s),1.42(9H,s),1.92

        ???(1H,br-s),1.96-2.02(2H,m),2.16-2.41(2H,m),

        ???2.30(3H,s),2.89(1H,d,J=4.4Hz),3.77(1H,d,

        ???J=7.4Hz),4.03-4.12(1H,m),4.35(1H,AB?type?d,

        ???J=8.8Hz),4.38(1H,AB?type?d,J=8.8Hz),4.63

        ???(1H,s),4.68(1H,d,J=8.3Hz),5.11(1H,s),5.30

        ???(1H,br-d,J=9.8Hz),5.52(1H,br-d,J=7.4Hz),

        ???5.74(1H,br-d,J=9.8Hz),6.06(1H,d,J=4.4Hz),

        ???6.10(1H,t,J=7.8Hz),7.35(2H,d,J=5.9Hz),

        ???7.47(2H,t,J=7.8Hz),7.60(1H,t,J=7.8Hz),

        ???8.10(2H,d,J=7.8Hz),8.59(2H,d,J=5.9Hz).FAB质谱:851(MH+)异构体BRf=0.25(氯仿∶甲醇=12∶1(v/v))熔点:160-163℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.29(3H,s),1.40(3H,s),1.59(3H,s),1.63(3H,

        ???s),1.68(3H,s),1.81(3H,s),1.40(9H,s),1.92

        ???(1H,br-s),2.05-2.42(4H,m),2.19(3H,5),2.93

        ???(1H,d,J=4.9Hz),3.83(1H,d,J=7.3Hz),4.03-

        ???4.13(1H,m),4.32(1H,AB?type?d,J=8.3Hz),4.39

        ???(1H,AB?type?d,J=8.3Hz),4.51(1H,br-s),4.73

        ???(1H,d,J=7.3Hz),5.18(1H,s?like),5.30(1H,

        ???br-d,J=8.4Hz),5.46-5.61(2H,m),6.06(1H,d,

        ???J=4.9Hz),6.23(1H,m),7.42(2H,d,J=6.8Hz),

        ???7.46(2H,t,J=7.6Hz),7.60(1H,t,J=7.6Hz),

        ???8.10(2H,d,J=7.6Hz),8.62(2H,d,J=6.8Hz).FAB质谱:851(MH+)本发明实施例4步骤1:9β-10-脱乙?;?9-二氢-9,10-O-(2-亚丙烯基)浆果赤霉素III

        用本发明实施例1步骤1中所得化合物作原料,重复本发明实施例1步骤2的反应过程,不同之处是用丙烯醛缩二乙醇代替2,2-二甲氧基丙烷,则得到标题化合物。Rf=0.30(氯仿∶丙酮=5∶1(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.17(3H,s),1.62(3H,s),1.65(3H,s),1.92(3H,

        ???s),1.82(1H,s),1.98(1H,dd,J=16.0Hz,6.8Hz),

        ???2.09-2.42(3H,m),2.34(3H,s),3.05(1H,d,J=

        ???4.4Hz),3.89(1H,d,J=6.8Hz),4.06-4.16(1H,m),

        ???4.32(1H,AB?type?d,J=8.2Hz),4.40(1H,AB?type?d,

        ???J=8.3Hz),4.59(1H,d,J=7.8Hz),4.82(1H,br-q,

        ???J=6.8Hz),5.07(1H,s),5.22(1H,d,J=6.3Hz),

        ???5.30(1H,d,J=6.8Hz),5.45(1H,d,J=10.3Hz),

        ???5.56(1H,d,J=17.6Hz),6.04(1H,d,J=4.4Hz),

        ???5.96-6.11(1H,m),7.48(2H,t,J=7.3Hz),7.60

        ???(1H,t,J=7.3Hz),8.13(2H,d,J=7.3Hz).步骤2:9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-(三异丙基甲硅烷氧基)丙?;?10-脱乙?;?9-二氢-9,10-O-(2-亚丙烯基)浆果赤霉素III

        用上述步骤1所得化合物作原料,重复本发明实施例1步骤3的反应过程则得到标题化合物。Rf=0.16(氯仿∶丙酮=12∶1(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.91-1.03(21H,m),1.30(3H,s),1.64(3H,s),

        ???1.68(3H,s),1.75(3H,s),1.40(9H,s),1.89(1H,

        ???s),2.21(2H,m),2.33(2H,d,J=8.8Hz),2.46(3H,

        ???s),2.96(1H,d,J=4.9Hz),3.91(1H,d,J=6.9Hz),

        ???4.05-4.14(1H,m),4.30(1H,AB?type?d,J=8.3Hz),

        ???4.40(1H,AB?type?d,J=8.3Hz),4.63(1H,d,J=

        ???8.3Hz),5.00(1H,s),5.12(1H,s),5.19(1H,d,J=

        ???6.4Hz),5.24(1H,d,J=6.9Hz),5.22-5.34(2H,m),

        ???5.45(1H,d,J=10.3Hz),5.57(1H,d,J=17.5Hz),

        ???5.94-6.15(2H,m),6.05(1H,d,J=4.9Hz),6.25

        ???(1H,d,J=2.9Hz),6.34(1H,dd,J=2.9Hz,1.9Hz),

        ???7.37(1H,d,J=1.9Hz),7.47(2H,t,J=7.8Hz),

        ???7.59(1H,t,J=7.8Hz),8.12(2H,d,J=7.8Hz).步骤3:9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?10-脱乙?;?9-二氢-9,10-O-(2-亚丙烯基)浆果赤霉素III

        用上述步骤2所得化合物作原料,重复本发明实施例1步骤4的反应过程则得到呈无色透明浆状的标题化合物。Rf=0.05(氯仿∶丙酮=12∶1(v/v))熔点:147-150℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.28(3H,s),1.62(3H,s),1.69(3H,s),1.71(3H,

        ???s),1.41(9H,s),2.05-2.26(3H,m),2.29-2.44

        ???(1H,m),2.35(3H,s),2.93(1H,d,J=4.9Hz),3.89

        ???(1H,d,J=6.8Hz),4.04-4.16(1H,m),4.32(1H,AB

        ???type?d,J=8.3Hz),4.39(1H,AB?type?d,J=8.3Hz),

        ???4.71(1H,s),5.10(1H,s),5.22(1H,d,J=5.9Hz),

        ???5.27(1H,d,J=6.8Hz),5.32-5.46(2H,m),5.46

        ???(1H,d,J=10.8Hz),5.57(1H,d,J=17.6Hz),5.97-

        ???6.19(2H,m),6.08(1H,d,J=4.9Hz),6.32(1H,d,

        ???J=1.9Hz),6.36(1H,dd,J=3.0Hz,1.9Hz),7.39

        ???(1H,d,J=3.0Hz),7.48(2H,t,J=7.8Hz),7.60

        ???(1H,t,J=7.8Hz),8.10(2H,d,J=7.8Hz).FAB质谱:838(MH+)本发明实施例5步骤1:9β-7-O-烯丙基-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-(三异丙基甲硅烷氧基)丙?;?10-脱乙?;?9-二氢-9,10-O-异亚丙基浆果赤霉素III

        于-50℃下将34.4mg本发明实施例1步骤3中所得化合物溶于1.4ml四氢呋喃中,向其中滴加1N六甲基二硅杂叠氮化钠(四氢呋喃溶液,0.14ml)。5分钟后,在相同温度下将所得溶液与0.020ml烯丙基碘混合并搅拌1.54小时,然后在-42℃下再与0.020ml烯丙基碘混合并搅拌1.5小时。在-40℃将该混合溶液与饱和氯化铵水液混合并用乙酸乙酯萃取。用饱和盐水洗涤该有机层并经无水硫酸钠干燥。之后,在减压下蒸发溶剂并用硅胶薄层色谱法(展开溶剂:己烷∶乙酸乙酯=5∶1(v/v))纯化所得残余物,则由Rf=0.12的胶面积上得到2.6mg无色透明浆状标题化合物,其中7位羟基被醚化了。

        另外,在Rf=0.27胶面积上得到4.2mg其中4位乙?;蛔上┍幕衔?。Rf=0.12(己烷∶乙酸乙酯=6∶1(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.90-1.02(m),1.22(3H,s),1.36(3H,s),1.38

        ???(9H,s),1.51(3H,s),1.53(3H,s),1.57(3H,s),

        ???1.77(3H,s),2.02-2.48(4H,m),2.44(3H,s),3.23

        ???(1H,d,J=5.8Hz),3.45(1H,dd,J=2.9Hz,9.8Hz),

        ???3.84(1H,dd,J=12.7Hz,5.4Hz),4.17(1H,dd,J=

        ???12.7Hz,5.4Hz),4.26(1H,AB?type?d,J=7.8Hz),4.56

        ???(1H,AB?type?d,J=7.8Hz),4.32(1H,d,J=8.8Hz),

        ???4.82(1H,t,J=6.4Hz),4.96(1H,s),5.14(1H,dd,

        ???J=10.3Hz,1.0Hz),5.21-5.36(2H,m),5.42(1H,d,

        ???J=8.8Hz),5.87(1H,d,J=5.8Hz),5.82-5.98(1H,

        ???m),6.14(1H,br-t,J=8.4Hz),6.24(1H,d,J=

        ???2.9Hz),6.34(1H,dd,J=2.9Hz,1.0Hz),7.37(1H,d,

        ???J=1.0Hz),7.47(2H,t,J=7.8Hz),7.56(1H,t,J=

        ???7.8Hz),8.10(2H,d,J=7.8Hz).步骤2:9β-7-O-烯丙基-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?10-脱乙?;?9-二氢-9,10-O-异亚丙基浆果赤霉素III

        用上述步骤1所得化合物作原料,重复本发明实施例1步骤4的反应过程则得到呈无色透明浆状的标题化合物。Rf=0.68(氯仿∶丙酮=12∶1(v/v))熔点:112-115℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.23(3H,s),1.25(3H,s),1.39(3H,s),1.40(9H,

        ???s),1.46-1.61(6H,m),1.73(3H,s),1.68-1.82

        ???(1H,m),2.08-2.40(3H,m),2.35(3H,s),3.12(1H,

        ???d,J=3.9Hz),3.44-3.56(1H,m),3.83(1H,dd,J=

        ???13.0Hz,6.0Hz),4.17(1H,dd,J=13.0Hz,4.8Hz),

        ???4.23(1H,d,J=7.8Hz),4.56(1H,d,J=8.3Hz),

        ???4.70(1H,d,J=3.5Hz),4.83(1H,t,J=4.9Hz),

        ???5.12(1H,d,J=8.8Hz),5.27(1H,d,J=16.1Hz),

        ???5.35(1H,br-s),5.46(1H,d,J=8.3Hz),5.82-5.98

        ???(1H,m),5.92(1H,d,J=3.9Hz),6.14(1H,br-t,J=

        ???8.4Hz),6.31(1H,d,J=2.9Hz),6.37(1H,dd,J=

        ???2.9Hz,1.5Hz),7.40(1H,d,J=1.5Hz),7.47(2H,t,

        ???J=7.8Hz),7.58(1H,t,J=7.8Hz),8.11(2H,d,J=

        ???7.8Hz).FAB质谱:880(M+)本发明实施例6步骤1:9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-(三异丙基甲硅烷氧基)丙?;?4,10-二脱乙?;?9-二氢-9,10-O-异亚丙基-4-O-(4-戊烯?;?浆果赤霉素III

        通过本发明实施例5步骤1的反应过程,由Rf=0.27胶面积上得到4.2mg的其中4位乙?;蛔上┍谋晏饣衔?。Rf=0.27(己烷∶乙酸乙酯=6∶1(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.91-1.04(m),1.23(3H,s),1.36(3H,s),1.37

        ???(9H,s),1.47(3H,s),1.50-1.60(6H,m),1.76(3H,

        ???s),2.09(1H,ddd,J=5.2Hz,8.8Hz,14.4Hz),2.15-

        ???2.31(2H,m),2.40(1H,dd,J=8.8Hz,15.2Hz),2.53-

        ???2.64(2H,m),2.71(1H,q,J=7.6Hz),2.87(1H,q,

        ???J=7.6Hz),3.18(1H,d,J=5.4Hz),3.92(1H,dd,

        ???J=8.8Hz,3.4Hz),4.26(1H,AB?type?d,J=8.3Hz),

        ???4.51(1H,AB?type?d,J=8.3Hz),4.41(1H,br-d,J=

        ???8.3Hz),4.76(1H,t,J=6.4Hz),4.96(1H,s),5.03

        ???(1H,q,J=10.8Hz),5.14(1H,dd,J=17.1Hz,

        ???1.0Hz),5.21-5.33(2H,m),5.40(1H,d,J=8.3Hz),

        ???5.81-5.97(1H,m),5.89(1H,d,J=5.4Hz),6.10

        ???(1H,t,J=8.8Hz),6.25(1H,d,J=3.4Hz),6.35

        ???(1H,dd,J=3.4Hz,2.8Hz),7.36(1H,d,J=2.8Hz),

        ???7.48(2H,t,J=7.3Hz),7.57(1H,t,J=7.3Hz),

        ???8.12(2H,d,J=7.3Hz).步骤2:9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?4,10-二脱乙?;?9-二氢-9,10-O-异亚丙基-4-O-(4-戊烯?;?浆果赤霉素III

        用上述步骤1所得化合物作原料,重复本发明实施例1步骤4的反应过程则得到标题化合物。Rf=0.20(氯仿∶丙酮=10=1(v/v))熔点:105-110℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.25(3H,s),1.28(3H,s),1.40(9H,s),1.58(3H,

        ???s),1.64(3H,s),1.67(3H,s),1.70(3H,s),2.07-

        ???2.28(3H,m),2.30-2.41(1H,m),2.49-2.66(3H,

        ???m),2.69-2.80(1H,m),2.94(1H,d,J=4.4Hz),

        ???3.66(1H,br-s),3.84(1H,d,J=5.4Hz),4.06(1H,

        ???m),4.33(1H,AB?type?d,J=8.3Hz),4.38(1H,AB

        ???type?d,J=8.3Hz),4.64-4.73(2H,m),4.99-5.10

        ???(2H,m),5.13(1H,dd,J=1.0Hz,17.0Hz),5.31(1H,

        ???s),5.54(1H,d,J=8.3Hz),5.75-5.89(1H,m),

        ???6.05(1H,d,J=4.4Hz),6.10(1H,br-t,J=7.2Hz),

        ???6.32(1H,d,J=3.4Hz),6.36(1H,dd,J=3.4Hz,

        ???1.5Hz),7.39(1H,d,J=1.5Hz),7.48(2H,t,J=7.4

        ???Hz),7.61(1H,t,J=7.4Hz),8.13(2H,d,J=

        ???7.4Hz).FAB质谱:880(M+)本发明实施例7步骤1:9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-(叔丁基二甲基甲硅烷氧基)-3-苯基丙?;?10-脱乙?;?9-二氢-9,10-O-(2-亚丙烯基)浆果赤霉素III

        用本发明实施例4步骤1中所得化合物作原料,按本发明实施例1步骤3所述相同方式进行原料与(3R,4S)-1-(叔丁氧基羰基)-3-(叔丁基二甲基甲硅烷氧基)-4-苯基氮杂环丁-2-酮的反应,则得到呈无色透明浆状的标题化合物。Rf=0.35(氯仿∶丙酮=7∶1(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???-0.33(3H,s),-0.11(3H,s),0.74(9H,s),1.33

        ???(3H,s),1.38(9H,s),1.64(3H,s),1.69(3H,s),

        ???1.73(3H,s),1.85(1H,s),2.13-2.28(3H,m),2.33

        ???(1H,dd,J=9.3Hz,14.6Hz),2.53(3H,s),2.96(1H,

        ???d,J=4.9Hz),3.91(1H,d,J=7.3Hz),4.04-4.14

        ???(1H,m),4.33(1H,AB?type?d,J=8.3Hz),4.40(1H,

        ???AB?type?d,J=8.3Hz),4.53(1H,s),4.59(1H,d,J=

        ???7.8Hz),5.13(1H,s),5.19(1H,d,J=5.9Hz),5.23

        ???(1H,d,J=7.3Hz),5.30(1H,br-d,J=8.8Hz),5.45

        ???(1H,d,J=10.3Hz),5.57(1H,d,J=17.6Hz),5.96-

        ???6.10(1H,m),6.04(1H,d,J=4.9Hz),6.20(1H,t,

        ???J=8.8Hz),7.18-7.41(5H,m),7.48(2H,t,J=

        ???7.8Hz),7.60(1H,t,J=7.8Hz),8.13(2H,d,J=

        ???7.8Hz).步骤2:9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?10-脱乙?;?9-二氢-9,10-O-(2-亚丙烯基)浆果赤霉素III

        用上述步骤1所得化合物作原料,重复本发明实施例1步骤4的反应过程则得到标题化合物。Rf=0.30(氯仿∶丙酮=5∶1(v/v))熔点:145-150℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.26(3H,s),1.40(9H,s),1.61(6H,s),1.68(3H,

        ???s),1.91(1H,s),2.00-2.36(3H,m),2.30(3H,s),

        ???2.39(1H,dd,J=9.8Hz,15.2Hz),2.90(1H,d,J=

        ???4.9Hz),3.85(1H,d,J=6.8Hz),4.06-4.15(1H,m),

        ???4.16(1H,br-s),4.32(1H,AB?type?d,J=8.8Hz),

        ???4.38(1H,AB?type?d,J=8.8Hz),4.57(1H,d,J=

        ???8.3Hz),4.62(1H,br-s),5.10(1H,s),5.22(1H,d,

        ???J=6.3Hz),5.26(1H,d,J=6.8Hz),5.30(1H,br-d,

        ???J=9.7Hz),5.97-6.13(2H,m),6.07(1H,d,J=

        ???4.3Hz),7.20-7.45(5H,m),7.47(2H,t,J=

        ???7.4Hz),7.60(1H,t,J=7.4Hz),8.10(2H,d,J=

        ???7.4Hz).FAB质谱:848(MH+)。本发明实施例8步骤1:9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?10-脱乙?;?9-二氢-9,10-O-(2,3-二羟基亚丙基)浆果赤霉素III

        于室温下将35.1mg本发明实施例4步骤3中所得化合物溶解在1.1ml四氢呋喃和0.35ml蒸馏水中,再将该溶液与26.8mg?N-吗啉-N-氧化物和4.8mg四氧化锇混合。21小时之后,将其与亚硫酸钠水液混合并用乙酸乙酯萃取。用饱和盐水洗涤该有机层并经无水硫酸钠干燥。之后,在减压下蒸发溶剂并用硅胶薄层色谱法(展开溶剂:氯仿∶甲醇=10∶1(v/v))纯化所得残余物,则得到14.1mg呈无色透明浆状的标题化合物。Rf=0.25(氯仿∶甲醇=8∶1(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.27(3H,s),1.29(3H,s),1.41(9H,s),1.63(3H,

        ???s),1.69(3H,s),1.70(3H,s),2.00-2.55(m),2.36

        ???(3H,s),2.93(1H,d,J=4.9Hz),3.70-4.00(m),

        ???4.05-4.18(1H,m),4.30(1H,AB?type?d,J=8.8Hz),

        ???4.38(1H,AB?type?d,J=8.8Hz),4.71(1H,s),4.75-

        ???4.92(2H,m),5.10(1H,s),5.26(1H,d,J=4.9Hz),

        ???5.35(1H,br-d,J=9.7Hz),6.03(1H,d,J=7.3Hz),

        ???6.08-6.16(1H,m),6.31(1H,d,J=3.4Hz),6.36

        ???(1H,dd,J=3.4Hz,1.5Hz),7.39(1H,d,J=1.5Hz),

        ???7.42-7.67(3H,m),8.02-8.17(2H,m).步骤2:9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?10-脱乙?;?9-二氢-9,10-O-(2-吗啉代亚乙基)浆果赤霉素III

        于室温将14.1mg上述步骤1所得的化合物溶于四氢呋喃-水-甲醇(1∶1∶1(v/v))混合溶剂中,并将该溶液与19.7mg偏高碘酸钠混合并搅拌30分钟。该溶液冷至0℃并与盐水混合,用乙酸乙酯萃取。在用饱和盐水洗涤所得萃取液并随后经无水硫酸钠干燥后,在减压下蒸发溶剂。在真空中干燥所得残余物并将其溶于1.3ml甲醇中,于室温下将所得溶液与0.10ml乙酸、0.14ml吗啉和13.9ml氰基硼氢钠混合并搅拌1小时。将该反应溶液与饱和碳酸氢钠水液和饱和盐水混合,并用乙酸乙酯萃取。所得萃取液用饱和盐水洗涤并经无水硫酸钠干燥。之后,在减压下蒸发溶剂并用硅胶薄层色谱法(展开溶剂:氯仿∶甲醇=12∶1(v/v))纯化所得残余物,则得到10.4mg呈无色透明浆状的标题化合物。Rf=0.56(氯仿∶丙酮=10∶1(v/v))熔点:149-152℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.27(3H,s),1.41(9H,s),1.60(3H,s),1.65(3H,

        ???s),1.69(3H,s),1.89(1H,s),2.08-2.26(3H,m),

        ???2.35(3H,s),2.31-2.43(1H,m),2.54-2.70(4H,

        ???m),2.74(1H,dd,J=5.4Hz,13.7Hz),2.82(1H,dd,

        ???J=3.9Hz,13.7Hz),2.92(1H,d,J=4.7Hz),3.69-

        ???3.79(4H,m),3.80(1H,d,J=6.9Hz),3.87-3.94

        ???(1H,broad),4.04-4.11(1H,m),4.31(1H,AB?type

        ???d,J=8.3Hz),4.39(1H,AB?type?d,J=8.3Hz),4.67

        ???(1H,d,J=8.3Hz),4.71(1H,s),5.02(1H,dd,J=

        ???5.4Hz,3.9Hz),5.11(1H,s),5.20(1H,d,J=6.9Hz),

        ??5.30-5.42(2H,m),6.04(1H,d,J=4.7Hz),6.11

        ??(1H,br-t,J=8.0Hz),6.31(1H,d,J=3.4Hz),6.36

        ??(1H,dd,J=3.4Hz,2.0Hz),7.39(1H,d,J=2.0Hz),

        ??7.48(2H,t,J=7.8Hz),7.60(1H,t,J=7.8Hz),

        ??8.11(2H,d,J=7.8Hz).FAB质谱:911(M+)。本发明实施例9步骤1:9β-10-脱乙?;?9-二氢-9,10-O-(2-亚丙烯基)-7-O-(2,2,2-三氯乙氧基羰基)浆果赤霉素III

        于0℃将100.4mg本发明实施例4步骤1中所得化合物溶于3.0ml吡啶中,随后向其中滴加0.025ml?2,2,2-三氯乙氧基碳酰氯。30分钟后向其中加入0℃的冷水并用乙酸乙酯萃取所得溶液。依次用1N盐酸、饱和碳酸氢钠水液和饱和盐水洗涤所得萃取液,并经无水硫酸钠干燥。之后在减压下蒸发溶剂并用硅胶柱色谱法(展开溶剂:氯仿∶丙酮=6∶1(v/v))纯化所得残余物,则得到116.7mg呈无色透明浆状的标题化合物。Rf=0.48(氯仿∶丙酮=5∶1(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.16(3H,s),1.60(3H,s),1.62(3H,s),1.96(3H,

        ???s),1.80(1H,s),1.91-2.00(1H,m),2.20(1H,dt,

        ???J=16.0Hz,4.4Hz),2.29-2.43(2H,m),2.35(3H,

        ???s),3.20(1H,d,J=4.9Hz),3.97(1H,d,J=7.3Hz),

        ???4.31(1H,AB?type?d,J=8.3Hz),4.44(1H,AB?type?d,

        ???J=8.3Hz),4.66(1H,AB?type?d,J=11.7Hz),4.83

        ???(1H,AB?type?d,J=11.7Hz),4.76-4.89(2H,m),

        ???5.15(1H,dd,J=5.3Hz,3.4Hz),5.19(1H,d,J=

        ???5.9Hz),5.34(1H,d,J=7.3Hz),5.46(1H,d,J=

        ???10.3Hz),5.57(1H,d,J=17.5Hz),5.98(1H,d,J=

        ???4.9Hz),6.04(1H,ddd,J=17.5Hz,10.3Hz,5.9Hz),

        ???7.48(2H,t,J=7.4Hz),7.59(1H,t,J=7.4Hz),

        ???8.13(2H,d,J=7.4Hz).步骤2:9β-13-O-〔3-(叔丁氧基羰基氨基)-2,2-二氟-3-(2-呋喃基)丙?;?10-脱乙?;?9-二氢-9,10-O-(2-亚丙烯基)-7-O-(2,2,2-三氯乙氧基羰基)浆果赤霉素III

        于室温下将0.2041g?3-(叔丁氧基羰基氨基)-2,2-二氟-3-(2-呋喃基)丙酸溶于4.0ml甲苯中,然后将该溶液与0.1516g碳酸联-2-吡啶基酯混合。20分钟后,加入2.0ml的0.1167g上述步骤1得到的化合物的甲苯悬浮液,再加入39.9mg?4-二甲基氨基吡啶,于65℃将该混合物搅拌16小时。冷至室温后,该反应溶液与水混合并用乙酸乙酯萃取。用饱和盐水洗涤所得萃取液并经无水硫酸钠干燥。之后,在减压下蒸发溶剂并用硅胶柱色谱法(展开溶剂:氯仿∶丙酮=20∶1(v/v))纯化所得残余物,则得到75.5mg呈无色透明浆状的标题化合物。Rf=0.44(氯仿∶丙酮=20∶1(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.28(3H,s),1.43(9H,s),1.47(3H,s),1.62(3H,

        ???s),1.64(3H,s),1.90(1H,broad?s),2.19-2.40

        ?(6H,m),3.13(1H,d,J=4.7Hz),3.95-4.01(1H,

        ?m),4.31(1H,AB?type?d,J=8.3Hz),4.39(1H,AB

        ?type?d,J=8.3Hz),4.67(1H,AB?type?d,J=

        ?11.7Hz),4.85(1H,AB?type?d,J=11.7Hz),4.87-

        ?4.94(1H,m),5.08-5.17(2H,m),5.28(1H,t,J=

        ?8.3Hz),5.38(1H,br-d,J=8.8Hz),5.46(1H,d,J=

        ?10.2Hz),5.56(1H,d,J=17.5Hz),5.58-5.73(1H,

        ?m),5.96(1H,d,J=4.7Hz),6.04(1H,ddd,J=

        ?17.5Hz,10.2Hz,5.9Hz),6.12-6.28(1H,m),6.31-

        ?6.46(2H,m),7.38-7.51(3H,m),7.60(1H,t,J=

        ?7.4Hz),8.06-8.14(2H,m).步骤3:9β-13-O-〔3-(叔丁氧基羰基氨基)-2,2-二氟-3-(2-呋喃基)丙?;?10-脱乙?;?9-二氢-9,10-O-(2-亚丙烯基)浆果赤霉素III

        将75.5mg上述步骤2得到的化合物溶于6.0ml乙酸-甲醇(1∶1(v/v))混合溶剂中,于室温该溶液与0.1728g的锌粉混合,并于62℃搅拌30分钟。将固体物滤掉。在减压下浓缩所得滤液,用乙酸乙酯稀释,用饱和碳酸氢钠水液和饱和盐水洗涤,然后经无水硫酸钠干燥。之后,在减压下蒸发溶剂并用硅胶薄层色谱法(展开溶剂:氯仿∶丙酮=7∶l(v/v))纯化所得残余物,则得到14.7mg呈无色透明浆状的标题化合物。Rf=0.30(氯仿∶丙酮=8∶l(v/v))熔点:124-127℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.30(3H,s),1.43(9H,s),1.62(6H,s),1.89(1H,

        ???s),2.16-2.35(4H,m),2.26(3H,s),2.92(1H,d,

        ???J=4.9Hz),3.83-3.94(1H,m),4.04-4.10(1H,m),

        ???4.28(1H,AB?type?d,J=8.3Hz),4.40(1H,AB?type?d,

        ???J=8.3Hz),4.60(1H,br-d,J=8.3Hz),5.12(1H,s),

        5.17-5.28(2H,m),5.31-5.41(1H,m),5.45(1H,

        d,J=10.7Hz),5.56(1H,d,J=17.6Hz),5.55-5.72

        (1H,m),5.94-6.07(1H,m),6.03(1H,d,J=4.9

        Hz),6.12-6.25(1H,m),6.35-6.46(2H,m),7.42

        (1H,s),7.48(2H,t,J=7.3Hz),7.60(1H,t,J=

        7.3Hz),8.06-8.14(2H,m).FAB质谱:858(M+)。本发明实施例10步骤1:9β-10-脱乙?;?9-二氢-9,10-O-异亚丙基-7-O-(2,2,2-三氯乙氧基羰基)浆果赤霉素III

        用本发明实施例1步骤2中所得化合物作原料,重复本发明实施例9步骤1的反应过程则得到呈无色透明浆状的标题化合物。Rf=0.33(氯仿∶丙酮=7∶1(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.16(3H,s),1.41(3H,s),1.56(3H,s),1.58(3H,

        ???s),1.59(3H,s),1.79(1H,s),1.89-2.01(1H,m),

        ???1.95(3H,s),2.04-2.13(1H,m),2.27-2.49(2H,

        ???m),2.35(3H,s),3.20(1H,d,J=4.9Hz),3.96(1H,

        ???d,J=7.3Hz),4.28(1H,AB?type?d,J=7.8Hz),4.51

        ???(1H,AB?type?d,J=7.8Hz),4.65(1H,AB?type?d,J=

        ???11.7Hz),4.80(1H,AB?type?d,J=11.7Hz),4.75-

        ???4.86(2H,m),5.08-5.13(1H,m),5.60(1H,d,J=

        ???7.3Hz),5.96(1H,d,J=4.9Hz),7.48(2H,t,J=

        ???7.3Hz),7.60(1H,t,J=7.3Hz),8.15(2H,d,J=

        ???7.3Hz).步骤2:9β-10-脱乙?;?9-二氢-9,10-O-异亚丙基-7-O-(2,2,2-三氯乙氧基羰基)-13-O-三乙基甲硅烷基浆果赤霉素III

        用上述步骤1所得化合物作原料,重复本发明实施例3的步骤2的反应过程,则得到呈无色透明晶体的标题化合物。Rf=0.45(己烷∶乙酸乙酯=3∶1(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.55-0.71(6H,m),1.01(9H,t,J=7.8Hz),1.20

        ???(3H,s),1.36(3H,s),1.52(3H,s),1.55(3H,s),

        ???1.58(3H,s),1.74(1H,s),1.88(3H,s),2.10(1H,

        ???dd,J=14.4Hz,8.8Hz),2.16-2.42(3H,m),2.28

        ???(3H,s),3.19(1H,d,J=5.4Hz),4.10(1H,d,J=

        ???8.3Hz),4.30(1H,AB?type?d,J=7.8Hz),4.47(1H,AB

        ???type?d,J=7.8Hz),4.67(1H,AB?type?d,J=11.7Hz),

        ???4.81(1H,AB?type?d,J=11.7Hz),4.90(1H,t,J=

        ???5.3Hz),4.96(1H,t,J=8.8Hz),5.04(1H,dd,J=

        ???7.9Hz,3.0Hz),5.49(1H,d,J=8.3Hz),5.84(1H,d,

        ???J=5.4Hz),7.47(2H,t,J=7.8Hz),7.59(1H,t,J=

        ???7.8Hz),8.11(2H,d,J=7.8Hz).步骤3:9β-10-脱乙?;?9-二氢-9,10-O-异亚丙基-13-O-三乙基甲硅烷基浆果赤霉素III

        用上述步骤2所得化合物,重复本发明实施例9的步骤3的反应过程,则得到呈白色泡沫的标题化合物。Rf=0.27(己烷∶乙酸乙酯=3∶1(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.58-0.75(6H,m),1.01(9H,t,J=7.8Hz),1.24

        ???(3H,s),1.40(3H,s),1.56(3H,s),1.62(6H,s),

        ???1.80(1H,s),1.86(3H,s),2.03-2.31(4H,m),2.27

        ???(3H,s),2.94(1H,d,J=4.9Hz),3.95(1H,d,J=

        ???7.9Hz),3.99-4.07(1H,m),4.28(1H,AB?type?d,J=

        ???8.3Hz),4.38(1H,AB?type?d,J=8.3Hz),4.61(1H,d,

        ???J=7.3Hz),4.97(1H,t,J=8.8Hz),5.10(1H,t,J=

        ???3.4Hz),5.52(1H,d,J=7.9Hz),5.95(1H,d,J=

        ???4.9Hz),7.47(2H,t,J=7.8Hz),7.59(1H,t,J=

        ???7.8Hz),8.12(2H,d,J=7.8Hz).步骤4:9β-7-O-烯丙基-10-脱乙?;?9-二氢-9,10-O-异亚丙基-13-O-三乙基甲硅烷基浆果赤霉素III

        于-50℃下将0.2400g上述步骤3所得化合物溶于7.2ml无水四氢呋喃中,再向其中滴加1.64N丁基锂(己烷溶液,0.315ml)。在滴加17分钟后,将所得溶液与溶于二甲亚砜(1.80ml)的烯丙基碘(0.15ml)混合,并于0℃搅拌该混合物1.5小时。于0℃将该混合溶液与饱和氯化铵水液混合并用乙酸乙酯萃取。所得萃取液用饱和盐水洗涤并经无水硫酸钠干燥。之后,在减压下蒸发溶剂并用硅胶柱色谱法(展开溶剂:己烷∶乙酸乙酯=10∶3(v/v))纯化所得残余物,则得到0.1358mg呈白色固体的标题化合物。Rf=0.41(己烷∶乙酸乙酯=3∶1(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.59-0.74(6H,m),1.01(9H,t,J=7.8Hz),1.37

        ???(3H,s),1.43(3H,s),1.50(3H,s),1.57(3H,s),

        ???1.65(1H,s),1.87(3H,s),2.00-2.14(2H,m),2.21

        ???-2.47(2H,m),2.28(3H,s),3.26(1H,d,J=

        ???5.8Hz),3.42(1H,dd,J=11.7Hz,3.4Hz),3.85(1H,

        ???dd,J=12.7Hz,5.4Hz),4.18(1H,dd,J=12.7Hz,

        ???5.4Hz),4.29(1H,AB?type?d,J=7.8Hz),4.54(1H,AB

        ???type?d,J=7.8Hz),4.40(1H,d,J=9.8Hz),4.82

        ???(1H,t,J=8.3Hz),4.93(1H,t,J=8.3Hz),5.16

        ???(1H,dd,J=10.3Hz,1.5Hz),5.32(1H,dd,J=

        ???17.1Hz,1.5Hz),5.41(1H,d,J=9.8Hz),5.77(1H,d,

        ???J=5.8Hz),5.85-6.00(1H,m),7.46(2H,t,J=

        ???7.3Hz),7.58(1H,t,J=7.3Hz),8.07(2H,d,J=

        ???7.3Hz).步骤5:9β-7-O-烯丙基-10-脱乙?;?9-二氢-9,10-O-异亚丙基浆果赤霉素III

        用上述步骤4所得化合物,重复本发明实施例1步骤4的反应过程,则得到呈无色透明浆状的标题化合物。Rf=0.05(己烷∶乙酸乙酯=2∶1(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.12(3H,s),1.40(3H,s),1.54(3H,s),1.55(3H,

        ???s),1.58(3H,s),1.74(1H,s),1.94(3H,s),1.99-

        ???2.38(4H,m),2.3(3H,s),3.22(1H,d,J=5.4Hz),

        ???3.57(1H,dd,J=6.9Hz,2.5Hz),3.83(1H,dd,J=

        ???12.4Hz,5.6Hz),4.09-4.27(2H,m),4.23(1H,d,J=

        ???7.7Hz),4.60(1H,d,J=7.7Hz),4.72-4.88(2H,m),

        ???5.11(1H,dd,J=10.3Hz,1.4Hz),5.26(1H,dd,J=

        ???17.0Hz,1.4Hz),5.52(1H,d,J=7.3Hz),5.81-5.96

        ???(2H,m),7.46(2H,t,J=7.8Hz),7.58(1H,t,J=

        ???7.8Hz),8.12(2H,d,J=7.8Hz).步骤6:9β-7-O-烯丙基-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-(叔丁基二甲基甲硅烷氧基)-3-苯基丙?;?10-脱乙?;?9-二氢-9,10-O-异亚丙基浆果赤霉素III

        用上述步骤5所得化合物,按照本发明实施例1的步骤3的反应过程进行该化合物与1-(叔丁氧基羰基)-3-(叔丁基二甲基甲硅烷氧基)-4-苯基氮杂环丁-2-酮的反应,则得到呈无色透明浆状的标题化合物。Rf=0.17(己烷∶乙酸乙酯=2∶1(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???-0.32(3H,s),-0.12(3H,s),0.74(9H,s),1.25(3H,

        ???s),1.36(3H,s),1.36(9H,s),1.51(3H,s),1.53

        ???(3H,s),1.57(3H,s),1.75(3H,s),2.06-2.12

        ???(2H,m),2.15-2.35(1H,m),2.42(1H,dd,J=

        ???14.7Hz,9.8Hz),2.53(3H,s),3.22(1H,d,J=

        ???5.9Hz),3.46(1H,dd,J=9,8Hz,2.0Hz),3.85(1H,

        ???dd,J=12.2Hz,5.4Hz),4.18(1H,dd,J=12.2Hz,

        ???5.8Hz),4.28(1H,AB?type?d,J=8.3Hz),4.58(1H,AB

        ???type?d,J=8.3Hz),4.33(1H,d,J=8.8Hz),4.50

        ???(1H,s),4.83(1H,t,J=6.8Hz),5.15(1H,dd,J=

        ???10.7Hz,1.4Hz),5.22-5.36(1H,m),5.31(1H,dd,J

        ???=17.2Hz,1.4Hz),5.40(1H,d,J=8.8Hz),5.41-

        ???5.54(1H,m),5.87(1H,d,J=5.9Hz),5.81-5.98

        ???(1H,m),6.22(1H,t,J=8.8Hz),7.19-7.42(5H,

        ???m),7.47(2H,t,J=7.3Hz),7.57(1H,t,J=7.3Hz),

        ???8.11(2H,d,J=7.3Hz).步骤7:9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-(叔丁基二甲基甲硅烷氧基)-3-苯基丙?;?10-脱乙?;?9-二氢-7-O-(2,3-二羟丙基)-9,10-O-异亚丙基浆果赤霉素III

        用上述步骤6所得化合物,重复本发明实施例8步骤1的反应过程则得到呈无色透明浆状标题化合物。Rf=0.29(氯仿∶丙酮=4∶1(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???-0.32(3H,s),-0.11(3H,s),0.74(9H,s),1.31

        ???(3H,s),1.37(9H,s),1.39(3H,s),1.52(3H,s),

        ???1.57(3H,s),1.60(3H,s),1.74(3H,s),1.94-2.42

        ???(m),2.53(3H,s),3.03?and?3.06(total?1H,each?d,

        ???J=4.9Hz),3.45-3.81(m),3.88-4.02(m),4.21-

        ???4.38(m),4.47(d,J=7.7Hz),4.50-4.58(m),

        ???4.90-5.01(m),5.23-5.36(m),5.40-5.54(m),

        ???5.92?and?5.94(total?1H,each?d,J=4.9Hz),5.94(d,

        ???J=4.9Hz),7.21-7.40(5H,m),7.48(2H,t,J=

        ???7.8Hz),7.59(1H,t,J=7.8Hz),8.13(2H,d,J=

        ???7.8Hz).步骤8:9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-(叔丁基二甲基甲硅烷氧基)-3-苯基丙?;?10-脱乙?;?9-二氢-7-O-(2-吗啉代乙基)-9,10-O-异亚丙基浆果赤霉素III

        用上述步骤7所得化合物,重复本发明实施例8步骤2的反应过程则得到呈无色透明浆状标题化合物。Rf=0.74(氯仿∶甲醇=12∶1(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???-0.33(3H,s),-0.12(3H,s),0.74(9H,s),1.26(3H,

        ???s),1.35(9H,s),1.39(3H,s),1.50(3H,s),1.52

        ???(3H,s),1.57(3H,s),1.74(3H,s),1.59-1.80(4H,

        ???m),2.05-2.33(3H,m),2.36-2.52(3H,m),2.52

        ???(3H,s),3.18(1H,d,J=5.4Hz),3.35-3.49(2H,

        ???m),3.60-3.84(5H,m),4.19-4.33(1H,m),4.26

        ???(1H,AB?type?d,J=8.3Hz),4.55(1H,AB?type?d,J=

        ???8.3Hz),4.50(1H,s),4.83(1H,t,J=6.4Hz),5.30

        ???(1H,br-d,J=8.0Hz),5.86(1H,d,J=5.4Hz),6.22

        ???(1H,t,J=8.8Hz),7.28-7.41(5H,m),7.48(2H,t,

        ???J=7.8Hz),7.58(1H,t,J=7.8Hz),8.11(2H,d,

        ???J=7.8Hz).步骤9:9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?10-脱乙?;?9-二氢-7-O-(2-吗啉代乙基)-9,10-O-异亚丙基浆果赤霉素III

        用上述步骤8所得化合物,重复本发明实施例1步骤4的反应过程,则得到呈无色透明浆状标题化合物。Rf=0.23(氯仿∶甲醇=15∶1(v/v))熔点:128-133℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.23(3H,s),1.39(9H,s),1.41(3H,s),1.51(3H,

        ???s),1.58(6H,s),1.59(3H,s),1.50-1.86(2H,m),

        ???1.81(1H,br-s),1.96-2.47(4H,m),2.30(3H,s),

        ???2.48-2.62(4H,m),3.03(1H,d,J=4.0Hz),3.32-

        ???3.43(1H,m),3.46-3.57(1H,m),3.59-3.84(4H,

        ???m),4.07-4.23(2H,m),4.52(1H,d,J=7.8Hz),

        ???4.60(1H,s)4.83(1H,s),5.22-5.33(1H,br-d,J=

        ???8.4Hz),5.46(1H,d,J=7.8Hz),5.59(1H,br-d,J=

        ???8.4Hz),5.93(1H,d,J=4.0Hz),6.10(1H,t,J=

        ???8.3Hz),7.21-7.43(5H,m),7.47(2H,t,J=7.8Hz),

        ???7.59(1H,t,J=7.8Hz),8.11(2H,d,J=7.8Hz).本发明实施例11步骤1:9β-13-O-〔(2R,3S)-N-(叔丁氧羰基)-N,O-(4-甲氧基亚苄基)-3-苯基异丝氨基〕-10-脱乙?;?9-二氢-9,10-O-(2-亚丙烯基)-7-O-(2,2,2-三氯乙氧基羰基)浆果赤霉素III

        于0℃将70.1mg(2R,3S)-N-(叔丁氧基羰基)-N,O-(4-甲氧基亚苄基)-3-苯基异丝氨酸溶于由2.1ml无水二氯甲烷和2.1ml无水甲苯组成的混合溶剂中,并将该溶液与34.0mg二环己基碳化二亚胺混合。在混合12分钟之后,向其中滴加2.5ml含78.1mg本发明实施例9步骤1所得化合物的无水二氯甲烷溶液,随后加入4.2mg4-二甲基氨基吡啶,并随后于室温搅拌2小时。在冷却至0℃后,过滤该反应混合物并用甲苯洗涤该滤过的物料。将所得滤液用氯仿稀释、用水和饱和盐水洗涤并经无水硫酸钠干燥。之后,在减压下蒸发溶剂并用硅胶薄层色谱法(展开溶剂:氯仿∶丙酮=20∶1(v/v))纯化所得残余物,则得到68.9mg呈白色玻璃质的标题化合物。Rf=0.18(氯仿∶丙酮=20∶1(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.05(12H,s),1.24(3H,s),1.45(3H,br-s),1.58

        ???(3H,s),1.74(3H,br-s),1.77(1H,s),2.07(1H,d,

        ??J=14.7Hz,J=8.3Hz),2.13-2.35(3H,m),3.04

        ??(1H,d,J=4.9Hz),3.81(3H,s),3.93(1H,d,J=

        ??7.8Hz),4.24(1H,d,J=8.3Hz),4.35(1H,d,J=

        ??8.3Hz),4.58(1H,d,J=4.9Hz),4.65(1H,d,J=

        ??11.7Hz),4.79(1H,t,J=4.9Hz),4.83(1H,d,J=

        ??11.7Hz),5.03(1H,dd,J=6.9Hz,J=4.0Hz),5.10

        ??(1H,d,J=5.9Hz),5.20(1H,d,J=7.8Hz),5.34-

        ??5.48(1H,br),5.45(1H,d,J=10.2Hz),5.55(1H,d,

        ??J=17.1Hz),5.87(1H,d,J=4.9Hz),5.93-6.1(2H,

        ??m),6.25-6.46(1H,br),6.90(2H,d,J=8.8Hz),

        ??7.32-7.52(7H,m),7.47(2H,t,J=7.3Hz),7.60

        ??(1H,t,J=7.3Hz),8.05(2H,d,J=7.3Hz).步骤2:9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?10-脱乙?;?9-二氢-9,10-O-亚丙基)-7-O-(2,2,2-三氯乙氧基羰基)浆果赤霉素III

        于室温下将68.9mg上述步骤1所得化合物溶于3.4ml乙醇中,并将该溶液与8.6mg的10%氢氧化钯混合,于氢气氛下搅拌5小时。然后,再将所得溶液与8.6mg?10%氢氧化钯混合并搅拌2小时。用氮气替代该反应体系的气氛并过滤该反应溶液。在用乙酸乙酯洗涤该滤过的物料后,在减压下蒸发该滤液中的溶剂并用硅胶薄层色谱法(展开溶剂:氯仿∶丙酮=20∶1(v/v))纯化所得残余物,则得到呈白色玻璃状的28.4mg标题化合物。Rf=0.40(氯仿∶丙酮=20∶1(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.03(3H,t,J=7.8Hz),1.25(3H,s),1.40(9H,s),

        ???1.59(3H,s),1.61(3H,s),1.64(3H,s),1.74-1.93

        ???(3H,m),2.01-2.23(2H,m),2.30(3H,s),2.30-

        ???2.45(2H,m),3.04(1H,d,J=4.9Hz),3.88(1H,d,

        ???J=7.3Hz),4.21-4.34(2H,m),4.43(1H,d,J=

        ???8.3Hz),4.62(1H,br-s),4.65(1H,d,J=12.2Hz),

        ???4.76(1H,t,J=5.4Hz),4.85(1H,d,J=12.2Hz),

        ???4.90(1H,br-s),5.14(1H,br-t,J=4.4Hz),5.24

        ???(1H,d,J=7.3Hz),5.31(1H,d,J=9.2Hz),5.66

        ???(1H,d,J=9.2Hz),6.00(1H,d,J=4.9Hz),6.09

        ???(1H,t,J=7.8Hz),7.20-7.46(5H,m),7.47(2H,t,

        ???J=7.3Hz),7.60(1H,t,J=7.3Hz),8.12(2H,d,J=

        ???7.3Hz).步骤3:9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?10-脱乙?;?9-二氢-9,10-O-亚丙基浆果赤霉素III

        将28.4mg上述步骤2所得化合物溶于2.8ml二噁烷-甲醇-乙酸(1∶1∶1(v/v))混合溶剂中,将该溶液与66.2mg锌粉混合并于室温搅拌5小时,再于55℃搅拌16小时。将该反应混合物过滤,用氯仿洗涤该滤过的物料,然后于减压下蒸发该滤液中的溶剂。用乙酸乙酯稀释所得残余物,用饱和碳酸氢钠水溶液和饱和盐水洗涤,然后经无水硫酸钠干燥。之后,在减压下蒸发溶剂并用硅胶薄层色谱法(展开溶剂:氯仿∶丙酮=10∶1(v/v))纯化所得残余物,则得到10.8mg的白色玻璃状的标题化合物。Rf=0.18(氯仿∶丙酮=20∶1(v/v))熔点:132-139℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.04(3H,t,J=7.9Hz),1.26(6H,s),1.40(9H,s),

        ???1.60(3H,s),1.66(3H,s),1.73-1.91(2H,m),1.88

        ???(1H,s),1.98-2.14(2H,m),2.17-2.33(1H,m),

        ???2.30(3H,s),2.37(1H,dd,J=15.1Hz,J=9.7Hz),

        ???2.91(1H,d,J=4.8Hz),3.78(1H,d,J=7.3Hz),

        ???4.02-4.19(2H,m),4.33(1H,d,J=8.3Hz),4.37

        ???(1H,d,J=8.3Hz),4.55-4.68(2H,m),4.80(1H,t,

        ??J=5.4Hz),5.10(1H,s?like),5.19(1H,d,J=

        ??7.3Hz),5.29(1H,br-d,J=8.3Hz),5.63(1H,br-d,

        ??J=8.3Hz),6.05(1H,d,J=4.8Hz),6.08(1H,t,J=

        ??8.8Hz),7.20-7.45(5H,m),7.47(2H,t,J=7.8Hz),

        ??7.60(1H,t,J=7.8Hz),8.10(2H,d,J=7.8Hz).FAB质谱:850(M++1)。本发明实施例12步骤1:9β-10-脱乙?;?9-二氢-9,10-O-异亚丙基-7-O-(4-硝基苯氧基羰基)浆果赤霉素III

        将70mg本发明实施例1步骤2所得化合物溶于2ml无水四氢呋喃中并冷至-78℃。在相同温度下然后向其中滴加0.16ml正丁基锂(1.64mol/ml的己烷溶液)。在滴加完成之后,于相同温度下搅拌该混合物10分钟。接着在相同温度下向其中滴加1ml含29mg氯甲酸4-硝苯酯的四氢呋喃溶液。搅拌1小时后,将该反应溶液逐渐升温至0℃并搅拌2小时。将该反应溶液与饱和氯化铵水液混合,并用乙酸乙酯稀释及萃取。所得萃取液用饱和盐水洗涤并经无水硫酸钠干燥。之后,在减压下蒸发溶剂,并用硅胶薄层色谱法纯化所得残余物(展开溶剂:氯仿∶丙酮=97∶3(v/v)),则得到23mg的标题化合物。1H-NMR(CDCl3/TMS)δ(ppm)

        ???1.18(3H,s),1.43(3H,s),1.57(3H,s),1.59(3H,

        ???s),1.62(3H,s),1.63-1.80(1H,m),1.90-2.09

        ???(2H,m),1.96(3H,s),2.25-2.41(1H,m),2.36(3H,

        ???s),3.18(1H,d,J=5Hz),3.94(1H,d,J=7Hz),

        ???4.18(1H,J=8Hz),4.25(1H,8Hz),4.78-4.89(1H,

        ???m),4.83-4.88(1H,m),5.13-5.17(1H,m),5.63

        ???(1H,d,J=7Hz),5.94(1H,d,J=5Hz),7.31(2H,d,

        ???J=9Hz),7.49(2H,t,J=8Hz),7.55-7.60(1H,m),

        ???8.12(2H,d,J=7Hz),8.21(2H,d,J=9Hz).步骤2:9β-10-脱乙?;?9-二氢-9,10-O-异亚丙基-7-O-〔(4-甲基哌嗪-1-基)羰基〕浆果赤霉素III

        于室温下将37mg上述步骤1所得化合物溶于2ml乙腈中,再向其中滴加50mg?N-甲基哌嗪。在相同温度搅拌5小时后,在减压下蒸发溶剂并用硅胶薄层色谱法(展开溶剂:氯仿∶甲醇=95∶5(v/v))纯化所得残余物,则得到9mg标题化合物。1H-NMR(CDCl3/TMS)δ(ppm)

        ???1.14(3H,s),1.38(3H,s),1.52(3H,s),1.55(3H,

        ???s),1.56(3H,s),1.68-1.80(1H,m),1.95(3H,s),

        ???2.01-2.16(2H,m),2.27(3H,s),2.24-2.38(5H,

        ???m),2.34(3H,s),3.24(1H,d,J=5Hz),3.30-3.57

        ???(4H,m),4.04(1H,d,J=8Hz),4.29(1H,J=8Hz),

        ???4.43(1H,8Hz),4.79-4.87(1H,m),4.84(1H,d,J=

        ???4Hz),5.16-5.19(1H,m),5.56(1H,d,J=8Hz),

        ???5.92(1H,d,J=5Hz),7.49(2H,t,J=8Hz),7.61

        ???(1H,t,J=8Hz),8.15(2H,d,J=7Hz).步骤3:9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-(叔丁基二甲基甲硅烷氧基)-3-苯基丙?;?10-脱乙?;?9-二氢-9,10-O-异亚丙基-7-O-〔(4-甲基哌嗪-1-基)羰基〕浆果赤霉素III

        用上述步骤2所得化合物作原料,依照本发明实施例1步骤3的反应过程进行该原料与1-(叔丁氧基羰基)-3-(叔丁基二甲基甲硅烷氧基)-4-苯基氮杂环丁-2-酮的反应,则得到呈白色非晶形固体的标题化合物。1H-NMR(CDCl3/TMS)δ(ppm)

        ???-0.33(3H,s),-0.12(3H,s),0.74(9H,s),1.25

        ???(3H,s),1.28(3H,s),1.33(6H,s),1.36(3H,s),

        ???1.53(3H,s),1.55(9H,s),1.63-1.80(1H,m),1.75

        ???(3H,s),2.00-2.20(2H,m),2.31(3H,s),2.20-

        ???2.45(5H,m),2.54(3H,s),3.21(1H,d,J=5Hz),

        ???3.39-3.64(4H,m),4.12(1H,d,J=9Hz),4.32(1H,

        ???d,J=8Hz),4.47(1H,d,J=8Hz),4.52(1H,brs),

        ???4.91(1H,m),5.10(1H,m),5.28-5.33(1H,m),5.44

        ???(1H,d,J=9Hz),5.42-5.49(1H,m),5.89(1H,d,

        ???J=5Hz),6.20-6.23(1H,m),7.23-7.40(5H,m),

        ???7.50(2H,t,J=8Hz),7.60(1H,t,J=8Hz),8.14

        ???(2H,d,J=8Hz).步骤4:9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?10-脱乙?;?9-二氢-9,10-O异亚丙基-7-O-〔(4-甲基哌嗪-1-基)羰基〕浆果赤霉素III

        于0℃将13mg上述步骤3所得化合物溶于1ml蒸馏过的吡啶中,随后向其中滴加0.2ml氟化氢-吡啶。在滴加完成后,将该溶液升温至室温并搅拌过夜。该反应溶液用水稀释并用乙酸乙酯萃取。用饱和盐水洗涤所得萃取液并经无水硫酸钠干燥。之后,在减压下蒸发溶剂并用硅胶薄层色谱法(展开溶剂:氯仿∶甲醇=95∶5(v/v))纯化所得残余物,则得到5mg标题化合物。1H-NMR(CDCl3/TMS)δ(ppm)

        ???1.24(3H,s),1.37(3H,s),1.39(3H,s),1.53(3H,

        s),1.56(9H,s),1.60-1.80(1H,m),1.62(3H,s),

        2.00-2.20(2H,m),2.20-2.42(5H,m),2.26(3H,

        s),2.32(3H,s),3.09(1H,d,J=5Hz),3.31-3.58

        (4H,m),4.03(1H,d,J=9Hz),4.27(1H,d,J=

        8Hz),4.41(1H,d,J=8Hz),4.62(1H,br-s),4.88

        (1H,m),5.16(1H,m),5.30(1H,m),5.49(1H,d,J=

        7Hz),5.59(1H,m),5.95(1H,m),6.10(1H,br-t,J=

        8Hz),7.23-7.40(5H,m),7.49(2H,t,J=8Hz),

        7.61(1H,t,J=7Hz),8.13(2H,d,J=7Hz).本发明实施例13步骤1:9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-(叔丁基二甲基甲硅烷氧基)-3-苯基丙?;?10-脱乙?;?9-二氢-9,10-O-异亚丙基-7-O-(2-二甲基氨基乙基)浆果赤霉素III

        用本发明实施例10步骤7中所得化合物作原料,重复本发明实施例8的步骤2的反应过程,不同之处是用二甲胺代替吗啉,由此得到呈白色玻璃状固体的标题化合物。Rf=0.53(氯仿∶甲醇=5∶1(v/v))??1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ?????-0.32(3H,s),-0.11(3H,s),0.75(9H,s),1.27

        ?????(3H,s),1.36(9H,s),1.40(3H,s),1.52(3H,s),

        ?????1.55(3H,s),1.57(3H,s),1.74(3H,s),2.09-2.26

        ?????(2H,m),2.31-2.51(8H,m),2.53(3H,s),2.63-

        ?????2.86(2H,m),3.13(1H,d,J=5.3Hz),3.46-3.63

        ?????(2H,m),3.76-3.89(1H,br),4.12-4.25(1H,br),

        ?????4.28(1H,d,J=7.8Hz),4.49(1H,d,J=7.8Hz),

        ?????4.52(1H,br),4.90(1H,t,J=4.4Hz),5.22-5.36

        ?????(1H,m),5.38-5.52(2H,m),5.88(1H,d,J=

        ?????5.3Hz),6.21(1H,t,J=8.5Hz),7.19-7.41(5H,m),

        ?????7.50(2H,t,J=7.4Hz),7.59(1H,t,J=7.4Hz),

        ?????8.11(2H,d,J=7.4Hz).

        步骤2:9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?10-脱乙?;?9-二氢-9,10-O-异亚丙基-7-O-(2-二甲基氨基乙基)浆果赤霉素III

        使用上述步骤1所得化合物,重复本发明实施例3步骤5的反应过程,则得到呈白色玻璃状固体的标题化合物。Rf=0.32(氯仿∶丙酮=20∶1(v/v))熔点:119-121℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.22(3H,s),1.38(9H,s),1.41(3H,s),1.51(3H,

        ???s),1.58(9H,s),1.80(1H,s),2.04-2.37(10H,m),

        ???2.26(3H,s),2.52(2H,t?like,J=5.9Hz),3.04(1H,

        ???d,J=4.4Hz),3.31-3.43(1H,m),3.46-3.57(1H,

        ???m),3.70-3.81(1H,m),4.14-4.28(1H,br),4.20

        ???(1H,d,J=7.8Hz),4.51(1H,d,J=7.8Hz),4.60

        ???(1H,s??like),4.84(1H,t?like,J=5.0Hz),5.27

        ???(1H,br-d,J=8.0Hz),5.46(1H,d,J=7.6Hz),5.59

        (1H,br-d,J=8.0Hz),5.92(1H,d,J=4.4Hz),6.10

        (1H,t,J=7.8Hz),7.21-7.43(5H,m),7.47(2H,t,

        J=7.8Hz),7.59(1H,t,J=7.8Hz),8.11(2H,d,J=

        7.8Hz).FAB质谱:921(M+)。本发明实施例14步骤1:9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-(叔丁基二甲基甲硅烷氧基)-3-苯基丙?;?10-脱乙?;?9-二氢-7-O-羧甲基-9,10-O-异亚丙基浆果赤霉素III

        于室温将67.2mg本发明实施例10步骤7中所得化合物溶于3ml四氢呋喃-甲醇-水(1∶1∶1(v/v))混合溶剂中,再将该溶液与55.3mg偏高碘酸钠混合并搅拌1小时。将该溶液与0℃的冷水混合并用乙酸乙酯萃取。用饱和盐水洗涤所得萃取液并经无水硫酸钠干燥。在减压下蒸发溶剂,将48.0mg所得残余物的22.0mg部分溶于1.65ml二噁烷和0.55ml水中,于室温与5.6mg氨基磺酸和5.3mg氯化钠混合,然后搅拌30分钟。将该反应溶液与水混合并用乙酸乙酯萃取。用饱和盐水洗涤所得萃取液并经无水硫酸钠干燥。之后,在减压下蒸发溶剂并用硅胶薄层色谱法(展开溶剂:氯仿∶甲醇=15∶1(v/v))纯化所得残余物,则得到21.3mg呈白色固体的标题化合物。Rf=0.39(氯仿∶甲醇=10∶1(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???-0.32(3H,s),-0.11(3H,s),0.74(9H,s),1.33(3H,

        ???s),1.37(9H,s),1.39(3H,s),1.58(6H,s),1.63

        ???(3H,s),1.74(3H,s),1.81(1H,s),2.02-2.40(4H,

        ???m),2.54(3H,s),3.04(1H,d,J=4.9Hz),3.68(1H,

        ???br),3.80-4.03(2H,m),4.33(1H,d,J=7.8Hz),

        ???4.54(1H,d,J=7.8Hz),4.44-4.62(1H,m),5.05

        ???(1H,br),5.30(1H,d,J=8.3Hz),5.45(1H,d,J=

        ???8.3Hz),5.52(1H,d,J=7.3Hz),5.94(1H,d,J=

        ???4.9Hz),6.20(1H,t,J=8.8Hz),7.18-7.42(5H,m),

        ???7.49(2H,t,J=7.9Hz),7.60(1H,t,J=7.9Hz),

        ???8.12(2H,d,J=7.9Hz).步骤2:9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?10-脱乙?;?7-O-羧甲基-9,10-O-异亚丙基浆果赤霉素III

        用上述步骤1所得化合物作原料,重复本发明实施例3步骤5的反应过程,则得到呈白色玻璃状固体的标题化合物。Rf=0.40(氯仿∶甲醇=10∶1(v/v))熔点:157-160℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.27(3H,s),1.40(3H,s),1.41(9H,s),1.53(3H,

        ???s),1.56(3H,s),1.58(3H,s),1.63(3H,s),1.86

        ???(1H,s),1.92-2.13(2H,m),2.26-2.44(2H,m),

        ???2.32(3H,s),2.95(1H,d,J=4.4Hz),3.71(1H,

        ???br-s),3.78(1H,br-d,J=6.0Hz),3.90(1H,d,J=

        ???6.6Hz),3.97-4.11(1H,br),4.29(1H,d,J=

        ???8.3Hz),4.30-4.44(1H,m),4.54(1H,d,J=8.3Hz),

        ???4.62(1H,br-s),5.04(1H,br-s),5.27(1H,d,J=

        8.3Hz),5.53(1H,d,J=6.8Hz),5.60(1H,d,J=

        8.3Hz),5.97(1H,d,J=4.4Hz),6.10(1H,t,J=

        7.8Hz),7.22-7.43(5H,m),7.47(2H,t,J=7.8Hz),

        7.60(1H,t,J=7.8Hz),8.10(2H,d,J=7.8Hz).

        FAB质谱:908(M++1)本发明实施例15步骤1:9β-13-O-〔3-(叔丁氧基羰基氨基)-2-甲基-2-三乙基甲硅烷氧基-3-苯基丙?;?10-脱乙?;?9-二氢-9,10-O-异亚丙基-7-O-三乙基甲硅烷基浆果赤霉素III

        用本发明实施例3步骤3所得化合物作原料,按本发明实施例1步骤3的反应过程进行该原料与顺-1-(叔丁氧基羰基)-3-甲基-4-苯基-3-(三乙基甲硅烷氧基)氮杂环丁-2-酮的反应,则得到呈无色玻璃状固体的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.50-0.72(12H,m),0.87(9H,t,J=8Hz),0.97

        ???(9H,t,J=8Hz),1.29(9H,s),1.34(3H,s),1.38

        ???(3H,s),1.41(3H,s),1.51(3H,s),1.57(3H,s),

        ???1.59(3H,s),1.73(3H,s),2.00-2.18(3H,m),2.34

        ???(1H,dd,J=15Hz,10Hz),2.64(3H,s),3.07(1H,d,

        ???J=5.5Hz),4.00(1H,dd,J=8Hz,3.5Hz),4.24(1H,

        ???d,J=8Hz),4.34(1H,br-d,J=8Hz),4.56(1H,d,

        ???J=8Hz),4.86(1H,t,J=5.5Hz),4.98(1H,d,J=

        ???10Hz),5.42(1H,d,J=9Hz),5.52(1H,d,J=10Hz),

        ???5.91(1H,d,J=5.5Hz),6.28(1H,t,J=9Hz),

        ???7.27-7.36(10H,m),7.48(2H,t,J=7.5Hz),7.58

        ???(1H,t,J=7.5Hz),8.15(2H,d,J=7.5Hz).步骤2:9β-13-O-〔3-(叔丁氧基羰基氨基)-2-羟基-2-甲基-3-苯基丙?;?10-脱乙?;?9-二氢-9,10-O-异亚丙基浆果赤霉素III

        按本发明实施例1步骤4所述相同方式进行上述步骤1所得化合物的反应,则得到呈无色玻璃状固体的标题化合物。熔点:180-182℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.32(3H,s),1.35(9H,s),1.40(6H,s),1.58(3H,

        ???s),1.60(3H,s),1.64(3H,s),1.68(3H,s),2.08-

        ???2.31(4H,m),2.51(3H,s),2.91(1H,d,J=4.5Hz),

        ???3.80(1H,d,J=7Hz),3.99(1H,s),4.08(1H,m),

        ???4.36(1H,AB?type?d,J=9Hz),4.39(1H,AB?type,J=

        ???9Hz),4.70(1H,d,J=8Hz),5.01(1H,d,J=10Hz),

        ???5.11(1H,br-s),5.50(1H,d,J=7Hz),5.67(1H,d,

        ???J=10Hz),6.05(1H,d,J=4.5Hz),6.22(1H,t,J=

        ???8Hz),7.28-7.41(10H,m),7.48(2H,t,J=7.5Hz),

        ???7.60(1H,t,J=7.5Hz),8.13(1H,d,J=7.5Hz).FAB质谱:865(M++1)。本发明实施例16步骤1:9β-13-O-〔(2R,3S)-N-(叔丁氧基羰基)-N,O-(4-甲氧基亚苄基)-3-苯基异丝氨基〕-10-脱乙?;?9-二氢-9,10-O-(亚丙烯基)浆果赤霉素III

        用本发明实施例11步骤1所得化合物作原料,重复本发明实施例11步骤3的反应过程,则得呈玻璃状固体的标题化合物。Rf=0.35(氯仿∶丙酮=15∶1(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.04(12H,s),1.27(3H,s),1.43(3H,brs),1.64

        ???(3H,s),1.72(3H,brs),1.83(1H,s),1.97-2.27(4H,m),2.82(1H,d,J=5.3Hz),3.81(3H,s),3.85(1H,d,J=7.4Hz),3.96-4.07(1H,m),4.22(1H,d,J=8.3Hz),4.32(1H,d,J=8.3Hz),4.48(1H,d,

        ???J=7.4Hz),4.58(1H,d,J=5.4Hz),4.98(1H,s

        ???like),5.17(2H,d,J=5.9Hz),5.32-5.49(1H,br),

        ???5.44(1H,d,J=10.8Hz),5.55(1H,d,J=17.8Hz),

        ???5.90-6.12(3H,m),6.22-6.47(1H,br),6.90(2H,

        ???d,J=8.8Hz),7.31-7.50(9H,m),7.59(1H,t,J=

        ???7.4Hz),8.03(2H,d,J=7.4Hz).步骤2:9β-13-O-〔(2R,3S)-N-(叔丁氧基羰基)-N,O-(4-甲氧基亚苄基)-3-苯基异丝氨基〕-10-脱乙?;?9-二氢-9,10-O-(2-N-吗啉代亚乙基)浆果赤霉素III

        于室温下将149.4mg上述步骤1所得化合物溶于由4.48ml四氢呋喃和1.49ml水组成的混合溶剂中,再将该溶液与87.2mg?N-甲基吗啉-N-氧化物和7.8mg四氧化锇混合,于黑暗中搅拌8小时,随后再加入3.6mg四氧化锇,再搅拌16小时。将该混合物溶液与亚硫酸钠水溶液混合,于室温搅拌10分钟然后用乙酸乙酯萃取。用饱和盐水洗涤所得萃取液并经无水硫酸钠干燥,并在减压下蒸发溶剂。将所得残余物溶于4.1ml四氢呋喃-水-甲醇(1∶1∶1(v/v))混合溶剂中,然后于室温下将溶液与118.6mg偏高碘酸钠混合并搅拌40分钟。将所得溶液冷至0℃,与冷水和饱和盐水混合,然后用乙酸乙酯萃取。用饱和盐水洗涤所得萃取液并经无水硫酸钠干燥。在减压下蒸发溶剂,将126.2mg所得残余物的65.2mg部分溶于4ml乙醇中,于室温下与0.04ml乙酸、0.059ml吗啉和14.0mg?10%氢氧化钯混合,然后在氢气氛下搅拌5小时。之后,用氮气代替该反应体系气氛,将所含物质滤出,在减压下蒸发所得滤液并用硅胶薄层色谱法(展开溶剂:氯仿∶丙酮=5∶1(v/v))纯化所得残余物,则得到18.4mg呈无色透明浆状的标题化合物。Rf=0.17(氯仿∶丙酮=5∶1(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ????1.04(3H,s),1.27(3H,s),1.41(3H,brs),1.56

        ????(3H,s),1.61(3H,s),1.71(3H,br-s),1.99-2.25

        ????(4H,m),2.52-2.86(7H,m),3.66-3.86(5H,m),

        ????3.81(3H,s),4.00(1H,br-s),4.21(1H,d,J=

        ????8.3Hz),4.32(1H,d,J=8.3Hz),4.57(1H,d,J=

        ????4.9Hz),4.92-5.03(2H,m),5.10(1H,d,J=7.4Hz),

        ????5.40(1H,br),5.93(1H,d,J=4.9Hz),6.05(1H,

        ????br),6.20-6.48(1H,br),6.90(2H,d,J=8.8Hz),

        ????7.31-7.51(9H,m),7.60(1H,t,J=7.3Hz),8.03

        ????(2H,d,J=7.3Hz).步骤3:9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?10-脱乙?;?9-二氢-9,10-O-(2-N-吗啉代亚乙基)浆果赤霉素III

        使用上述步骤2所得化合物,重复本发明实施例11步骤2的反应过程,则得到呈无色透明浆状的标题化合物。Rf=0.20(氯仿∶丙酮=15∶1(v/v))熔点:129-132℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.26(6H,s),1.40(9H,s),1.59(3H,s),1.65(3H,

        ???s),1.88(1H,s),1.96-2.46(4H,m),2.30(3H,s),

        ???2.50-2.70(4H,m),2.74(1H,dd,J=18.4Hz,J=

        ???4.4Hz),2.83(1H,dd,J=18.4Hz,J=4.4Hz),2.90

        ???(1H,d,J=4.9Hz),3.63-3.86(5H,m),4.02-4.18

        ???(2H,m),4.32(1H,d,J=8.3Hz),4.38(1H,d,J=

        ???8.3Hz),4.63(1H,s?1ike),4.56(1H,d,J=8.3Hz),

        ???5.02(1H,t,J=3.9Hz),5.10(1H,s?1ike),5.19(1H,

        ???d?like,J=6.9Hz),5.29(1H,d,J=10.0Hz),5.61

        ???(1H,d,J=10.0Hz),6.00-6.13(2H,m),7.19-7.53

        ???(7H,m),7.59(1H,t,J=7.3Hz),8.11(2H,d,J=

        ???7.3Hz).FAB质谱:921(M+)。

        按相同方式合成下列化合物。本发明实施例179β-9,10-O-(2-苄氨基亚乙基)-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?10-脱乙?;?9-二氢浆果赤霉素III熔点:125-128℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.25(3H,s),1.40(9H,s),1.56(6H,s),1.63(3H,s),

        ???1.80-2.45(5H,m),2.30(3H,s),2.89(1H,d,J=

        ???4.9Hz),2.99(2H,d,J=4.9Hz),3.80(1H,d,J=

        ???6.8Hz),3.88(2H,s),4.08(1H,brs),4.31(1H,d,J=

        ???8.3Hz),4.37(1H,d,J=8.3Hz),4.62(1H,s),5.00

        ???(1H,t,J=4.9Hz),5.10(1H,s),5.21(1H,d,J=

        ???6.8Hz),5.29(1H,d,J=8.8Hz),5.64(1H,d,J=

        ???8.8Hz),6.00-6.15(2H,m),7.22-7.56(7H,m),7.60

        ???(1H,t,J=7.3Hz),8.10(2H,d,J=7.3Hz).FAB质谱:941(M+)。本发明实施例189β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?10-脱乙?;?9-二氢-9,10-O-〔2-(4-硫代吗啉基)亚乙基〕浆果赤霉素III熔点:149-152℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.26(3H,s),1.40(9H,s),1.56(3H,s),1.58(3H,s),

        ???1.64(3H,s),1.88(1H,s),2.00-2.45(3H,m),2.30

        ???(3H,s),2.62-2.96(11H,m),3.77(1H,d,J=7.3Hz),

        ???4.03-4.21(2H,m),4.31(1H,d,J=8.8Hz),4.38(1H,

        ???d,J=8.8Hz),4.57-4.70(2H,m),4.99(1H,t,J=

        ???4.9Hz),5.10(1H,s),5.18(1H,d,J=6.9Hz),5.29

        ???(1H,d,J=8.3Hz),5.62(1H,d,J=8.3Hz),6.00-

        ???6.17(2H,m),7.23-7.46(7H,m),7.60(1H,t,J=

        ???7.4Hz),8.10(2H,d,J=7.4Hz).FAB质谱:937(MH+)。本发明实施例199β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?10-脱乙?;?9-二氢-9,10-O-(2-二甲基氨基亚乙基)浆果赤霉素III熔点:148-149℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.24(3H,s),1.38(9H,s),1.55(3H,s),1.58(3H,s),

        ???1.64(3H,s),1.87(1H,s),1.9-2.43(4H,m),2.28

        ???(3H,s),2.35(6H,s),2.67(1H,dd,J=13.2Hz,J=

        ???7.8Hz),2.75(1H,dd,J=13.2Hz,J=3.4Hz),2.88(1H,

        ???d,J=4.9Hz),3.76(1H,d,J=7.3Hz),4.07(1H,br

        ???s),4.30(1H,d,J=8.8Hz),4.36(1H,d,J=8.8Hz),

        ???4.60(2H,brs),4.98(1H,dd,J=5.4Hz,J=3.4Hz),

        ???5.08(1H,s),5.18(1H,d,J=7.3Hz),5.27(1H,d,J=

        ???9.3Hz),5.61(1H,d,J=9.3Hz),6.00-6.18(2H,m),

        ???7.20-7.55(7H,m),7.60(1H,t,J=7.8Hz),8.09(2H,

        ???d,J=7.8Hz).FAB质谱:879(MH+)。本发明实施例209β-4-O-丁?;?13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?4,10-二脱乙?;?9-二氢-9,10-O-(2-亚丙烯基)浆果赤霉素III熔点:125-128℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.02(3H,t,J=7.3Hz),1.28(3H,s),1.41(9H,s),

        ???1.62(3H,s),1.69(3H,s),1.71(3H,s),1.75-1.94

        ???(2H,m),1.81(1H,s),2.10-2.28(3H,m),2.29-2.52

        ???(3H,m),2.54-2.68(1H,m),2.94(1H,d,J=4.9Hz),

        ???3.79-3.95(1H,br),3.89(1H,d,J=6.8Hz),4.04-

        ???4.16(1H,m),4.32(1H,d,J=8.7Hz),4.39(1H,d,J=

        ???8.7Hz),4.59(1H,d,J=8.3Hz),4.70(1H,s),5.05

        ???(1H,s),5.21(1H,d,J=5.8Hz),5.27(1H,d,J=

        ???6.8Hz),5.27-5.40(2H,m),5.46(1H,d,J=10.2Hz),

        ???5.57(1H,d,J=17.5Hz),6.04(1H,ddd,J=17.5Hz,

        ???J=10.2Hz,J=5.8HZ),6.08(1H,d,J=4.9Hz),6.05-

        ???6.15(1H,m),6.33(1H,d,J=2.9Hz),6.36(1H,dd,

        ???J=2.9Hz,J=1.9Hz),7.39(1H,d,J=1.9Hz),7.47

        ???(2H,t,J=7.8Hz),7.61(1H,t,J=7.8Hz),8.12(2H,

        ???d,J=7.8Hz).FAB质谱:866(MH+)。本发明实施例219β-4-O-丁?;?13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?4,10-二脱乙?;?9-二氢-9,10-O-(2-亚丙烯基)浆果赤霉素III熔点:127-130℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.99(3H,t,J=7.3Hz),1.26(3H,s),1.29(3H,s),

        ???1.40(3H,s),1.61(3H,s),1.67(3H,s),1.73-1.88

        ???(2H,m),1.92(1H,brs),2.00-2.46(3H,m),2.91

        ???(1H,d,J=4.9Hz),3.86(1H,d,J=6.8Hz),4.09(1H,

        ???brs),4.32(1H,d,J=8.8Hz),4.38(1H,d,J=

        ???8.8Hz),4.50-4.68(2H,m),5.04(1H,s?like),5.21

        ???(1H,d,J=6.4Hz),5.21-5.32(2H,m),5.45(1H,d,

        ???J=10.7Hz),5.56(1H,d,J=17.1Hz),5.62(1H,d,J=

        ???9.8Hz),5.97-6.12(3H,m),7.22-7.52(7H,m),7.60

        ???(1H,t,J=7.8Hz),8.11(2H,d,J=7.8Hz).FAB质谱:876(MH+)。本发明实施例229β-4-O-丁?;?13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?4,10-二脱乙?;?9,10-O-(2-吗啉代亚乙基)浆果赤霉素III熔点:123-125℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.01(3H,t,J=7.3Hz),1.27(3H,s),1.40(9H,s),

        ???1.61(3H,s),1.65(3H,s),1.69(3H,s),1.77-1.92

        ???(2H,m),1.88(1H,s),2.08-2.26(2H,m),2.31-2.60

        ???(7H,m),2.74(1H,dd,J=18.0Hz,J=4.4Hz),2.83

        ???(1H,dd,J=18.0Hz,J=4.0Hz),2.93(1H,d,J=

        ???4.9Hz),3.73(4H,t,J=4.9Hz),3.82(1H,d,J=

        ???6.9Hz),4.05-4.12(1H,m),4.31(1H,d,J=8.3Hz),

        ???4.39(1H,d,J=8.3Hz),4.64-4.73(2H,m),5.02(1H,

        ???t,J=4.0Hz),5.06(1H,s?like),5.20(1H,d,J=

        ???6.9Hz),5.33(2H,s),6.04(1H,d,J=4.9Hz),6.08(1H,

        ???br?t,J=8.0Hz),6.33(1H,d,J=3.5Hz),6.36(1H,

        ???dd,J=3.5Hz,J=1.9Hz),7.39(1H,d,J=1.9Hz),

        ???7.48(2H,t,J=7.8Hz),7.61(1H,t,J=7.8Hz),8.12

        ???(2H,d,J=7.8Hz).FAB质谱:939(MH+)。本发明实施例239β-4-O-丁?;?13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?4,10-二脱乙?;?9,10-O-(2-吗啉代亚乙基)浆果赤霉素III熔点:130-132℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.99(3H,t,J=7.3Hz),1.26(3H,s),1.40(9H,s),

        ???1.60(3H,s),1.64(3H,s),1.72-1.79(2H,m),1.80

        ???(1H,s),2.01-2.26(3H,m),2.30-2.43(2H,m),2.49

        ???-2.70(5H,m),2.75(1H,dd,J=13.2Hz,J=4.9Hz),

        ???2.83(1H,dd,J=13.2Hz,J=3.9Hz),2.89(1H,d,J=

        ???4.4Hz),3.74(4H,t,J=4.4Hz),3.78(1H,d,J=

        ???7.4Hz),4.01-4.12(2H,m),4.32(1H,d,J=8.7Hz),

        ???4.38(1H,d,J=8.7Hz),4.62(1H,br?s),4.66(1H,d,

        ???J=8.3Hz),4.99-5.09(2H,m),5.19(1H,d,J=

        ???6.8Hz),5.27(1H,d,J=9.3Hz),5.60(1H,d,J=

        ???9.3Hz),5.60(1H,d,J=9.3Hz),5.98-6.10(2H,m),

        ???7.20-7.52(7H,m),7.61(1H,t,J=7.3Hz),8.12(2H,

        ???d,J=7.3Hz).FAB质谱:949(MH+)。本发明实施例249β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?4,10-二脱乙?;?9-二氢-4-O-丙?;?9,10-O-(2-亚丙烯基)浆果赤霉素III熔点:135-137℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.29(3H,s),1.34(3H,t,J=7.8Hz),1.40(9H,s),

        ???1.63(3H,s),1.69(3H,s),1.71(3H,s),1.90(1H,s),

        ???2.10-2.26(3H,m),2.31-2.44(1H,m),2.51-2.73

        ???(2H,m),2.94(1H,d,J=4.9Hz),3.91(1H,d,J=

        ???7.4Hz),4.09(1H,br),4.32(1H,d,J=8.8Hz),4.40

        ???(1H,d,=8.8Hz),4.55(1H,br?d,J=7.4Hz),4.69(1H,

        ???s),5.03(1H,s?like),5.21(1H,d,J=5.9Hz),5.26

        ???(1H,d,J=7.4Hz),5.29-5.39(2H,m),5.45(1H,d,

        ???J=10.7Hz),5.57(1H,d,J=17.6Hz),5.97-6.06(3H,

        ???m),6.33(1H,d,J=2.9Hz),6.36(1H,dd,J=2.9Hz,

        ???J=2.0Hz),7.39(1H,d,J=2.0Hz),7.47(2H,t,J=

        ???7.8Hz),7.60(1H,t,J=7.8Hz),8.13(2H,d,J=

        ???7.8Hz).FAB质谱:852(MH+)。本发明实施例259β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?4,10-二脱乙?;?9-二氢-9,10-O-(2-吗啉代亚乙基)-4-O-丙?;嗝顾豂II熔点:145-148℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.28(3H,s),1.32(3H,t,J=7.6Hz),1.40(9H,s),

        ???1.61(3H,s),1.66(3H,s),1.70(3H,s),1.89(1H,s),

        ???2.09-2.26(3H,m),2.51-2.70(6H,m),2.75(1H,dd,

        ???J=12.4Hz,J=5.6Hz),2.82(1H,dd,J=12.4Hz,J=

        ???4.0Hz),2.93(1H,d,J=4.9Hz),3.74(4H,t,J=

        ???4.4Hz),3.83(1H,d,J=7.4Hz),4.04-4.12(1H,m),

        ???4.32(1H,d,J=8.3Hz),4.41(1H,d,J=8.3Hz),4.66

        ???(1H,d,J=8.3Hz),4.66(1H,s),4.99-5.08(2H,m),

        ???5.20(1H,d,J=7.4Hz),5.32(2H,s?like),6.05(1H,

        ???d,J=4.9Hz),6.10(1H,br?t,J=7.8Hz),6.33(1H,d,

        ???J=3.4Hz),6.36(1H,dd,J=3.4Hz,J=2.0HZ),7.39

        ???(1H,d,J=2.0Hz),7.48(2H,t,J=7.8Hz),7.61(1H,

        ???t,J=7.8Hz),8.13(2H,d,J=7.8Hz).FAB质谱:925(MH+)。本发明实施例269β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?4,10-二脱乙?;?9-二氢-9,10-O-(2-亚丙烯基)-4-O-丙?;嗝顾豂II熔点:190-192℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.27(3H,s),1.30(3H,t,J=7.8Hz),1.40(9H,s),

        ???1.59(6H,br?s),1.61(3H,s),1.68(3H,s),1.90(1H,

        ???s),2.02-2.24(3H,m),2.29-2.70(4H,m),2.91(1H,

        ???d,J=4.4Hz),3.87(1H,d,J=6.9Hz),3.99-4.16

        ???(2H,m),4.32(1H,d,J=8.3Hz),4.40(1H,d,J=

        ???8.3Hz),4.55(1H,d,J=8.3Hz),4.61(1H,br?s),5.03

        ???(1H,s?like),5.19-5.32(1H,m),5.21(1J,d,J=

        ???6.4Hz),5.25(1H,d,J=6.9Hz),5.45(1H,d,J=

        ???10.7Hz),5.50-5.62(1H,m),5.56(1H,d,J=17.1Hz),

        ???5.99-6.13(3H,m),7.12-7.50(7H,m),7.60(1H,t,

        ???J=7.3Hz),8.12(2H,d,J=7.3Hz).FAB质谱:862(MH+)。

        本发明实施例27

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?4,10-二脱乙?;?9-二氢-9,10-O-(2-吗啉代亚乙基)-4-O-丙?;嗝顾豂II

        熔点:137-139℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ????1.25(3H,s),1.27(3H,s),1.29(3H,t,J=7.3Hz),

        ????1.39(9H,s),1.58(3H,s),1.65(3H,s),1.88(1H,s),

        ????2.02-2.26(3H,m),2.36(1H,dd,J=14.0Hz,J=

        ????10.0Hz),2.42-2.71(4H,m),2.75(1H,dd,J=14.0Hz,

        ???J=4.8Hz),2.83(1H,dd,J=14.0Hz,J=3.8Hz),2.90

        ???(1H,d,J=4.4Hz),3.74(1H,t,J=4.4Hz),3.79(1H,

        ???d,J=6.8Hz),3.92-4.13(2H,br),4.32(1H,d,J=

        ???8.8Hz),4.40(1H,d,J=8.8Hz),4.56-4.67(2H,m),

        ???5.03(1H,s?like),5.19(1H,d,J=6.8Hz),5.22(1H,

        ???br?d,J=9.2Hz),5.55(1H,d,J=9.2Hz),5.98-6.12

        ???(2H,m),7.11-7.50(7H,m),7.61(1H,t,J=7.3Hz),

        ???8.12(2H,d,J=7.3Hz).

        FAB质谱:935(MH+)。

        本发明实施例28

        9β-13-O-〔(3S)-3-(叔丁氧基羰基氨基)-2,2-二氟-3-(2-呋喃基)丙?;?10-脱乙?;?9-二氢-9,10-O-(2-亚丙烯基)浆果赤霉素III

        熔点:176-178℃(由二噁烷冷冻干燥)lH-NMR(400?MHz,CDCl3/TMS)δ(ppm)????

        ???1.30(s),1.44(9H,s),1.62(s),1.69(s),2.32(s),

        ???2.93(1H,d,J=5Hz),3.89(1H,d,J=7Hz),4.08(1H,

        ???m),4.28(1H,d,J=8.5Hz),4.40(1H,d,J=8.5Hz),

        ???4.61(1H,d,J=8.5Hz),5.13(1H,br),5.20(1H,d,

        ???J=6Hz),5.23(1H,d,J=7Hz),5.38(1H,d,J=

        ???12Hz),5.45(1H,d,J=11Hz,),5.56(1H,d,J=

        ???17Hz),5.67(1H,m),6.03(2H,m),6.21(1H,t,J=

        ???9Hz),6.39(1H,dd,J=3Hz,2Hz),6.44(1H,d,J=

        ???3Hz),7.43(1H,d,J=2Hz),7.48(2H,t,J=7.5Hz),

        ???7.61(1H,t,J=7.5Hz),8.11(2H,d,J=7.5Hz).

        FAB质谱:858(M+)。

        本发明实施例29

        9β-13-O-〔(3S)-3-(叔丁氧基羰基氨基)-2,2-二氟-3-(2-呋喃基)丙?;?10-脱乙?;?9-二氢-9,10-O-(2-吗啉代亚乙基)浆果赤霉素III

        熔点:142-144℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.30(s),1.44(9H,s),1.61(s),1.66(s),2.19(2H,

        ???m),2.28(2H,m),2.32(3H,s),2.62(4H,m),2.74(1H,

        ???dd,J=13.5Hz,5Hz),2.81(1H,dd,J=13.5Hz,5Hz),

        ???2.91(1H,d,J=5Hz),3.73(4H,t,J=4.5Hz),3.81

        ???(1H,d,J=7.5Hz),4.07(1H,br),4.28(1H,d,J=

        ???8.5Hz),4.41(1H,d,J=8.5Hz),4.72(1H,d,J=

        ???8.5Hz),5.01(1H,t,J=4.5Hz),5.14(1H,br),5.16

        ???(1H,d,J=7.5Hz),5.38(1H,d,J=9Hz),5.67(1H,

        ???m),6.01(1H,d,J=5Hz),6.20(1H,t,J=9Hz),6.39

        ???(1H,dd,J=3Hz,2Hz),6.43(1H,d,J=3Hz),7.43

        ???(1H,d,J=2Hz),7.49(2H,t,J=7.5Hz),7.61(1H,t,

        ???J=7.5Hz),8.11(2H,d,J=7.5Hz).

        FAB质谱:931(M+)。

        本发明实施例30

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)--2-羟基-3-苯基丙?;?10-脱乙?;?9-二氢-7-O-甲基-9,10-O-(2-亚丙烯基)浆果赤霉素III

        熔点:137-140℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDC13/TMS)δ(ppm)

        ???1.20(3H,s),1.40(9H,br?s),1.57(3H,s),1.59(3H,

        ???s),1.65(3H,s),1.86(1H,s),1.95-2.50(4H,m),

        ???2.27(3H,s),3.07(1H,d,J=4.9Hz),3.33-3.42(1H,

        ???s),3.38(3H,s),4.29(1H,d,J=8.1Hz),4.32-4.40

        ???(1H,br),4.36(1H,d,J=8.1Hz),4.46(1H,d,J=

        ???7.8Hz),4.62(1H,br?s),4.89(1H,br?d,J=5.4Hz),

        ???5.17(1H,d,J=5.9Hz),5.25-5.38(1H,m),5.34(1H,

        ???d,J=8.3Hz),5.48(1H,d,J=10.3Hz),5.59(1H,d,J

        ???=17.6Hz),5.66(1H,br?d,J=9.3Hz),5.96(1H,d,J=

        ???4.9Hz),6.08(1H,br?t,J=7.8Hz),6.17(1H,ddd,J=

        ???5.9,10.3,17.6Hz),7.26-7.44(5H,m),7.46(2H,t,J

        ???=7.3Hz),7.59(1H,t,J=7.3Hz),8.09(2H,d,J=

        ???7.3Hz).

        FAB质谱:862(MH+)。

        本发明实施例31

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)--2-羟基-5-甲基-4-己?;?10-脱乙?;?9-二氢-9,10-O-(2-亚丙烯基)浆果赤霉素III

        熔点:122-127℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.25(3H,s),1.40(9H,s),1.62(3H,s),1.69(3H,s),

        ???1.75(6H,s),1.77(3H,s),2.04-2.38(4H,m),2.11

        ???(3H,s),2.63(1H,s),2.96(1H,d,J=7.5Hz),4.11

        ???(1H,m),4.29(1H,br),4.36(2H,ABq,J=8.5Hz),

        ???4.58(1H,d,J=8.2Hz),4.83(1H,dt,J=9.1Hz,

        ???2.3Hz),4.96(1H,br),5.12(1H,s),5.22(1H,d,J=

        ???6.1Hz),5.27(1H,d,J=7.9Hz),5.28(1H,d,J=

        ???6.1Hz),5.45(1H,d,J=10.5Hz),5.57(1H,d,J=

        ???17.1Hz),5.94-6.12(3H,m),7.46(2H,t,J=7.8Hz),

        ???7.50(1H,t,J=7.3Hz),8.04(2H,d,J=6.8Hz).

        FAB质谱:826(MH+)。

        本发明实施例32

        9β-9,10-O-〔(2E)-4-苄氧基-2-亚丁烯基〕-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)--2-羟基-3-苯基丙?;?10-脱乙?;?9-二氢浆果赤霉素III

        熔点:112-115℃(由二噁烷冷冻干燥)??1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ?????1.25(3H,s),1.40(9H,s),1.59(3H,br?s),1.62(3H,

        ?????s),1.68(3H,s),1.90(1H,s),2.00-2.35(3H,m),

        ?????2.29(3H,s),2.37(1H,dd,J=15.2Hz,J=9.8Hz),

        ?????2.90(1H,d,J=4.4Hz),3.85(1H,d,J=6.9Hz),4.10

        ?????(2H,d,J=4.4Hz),4.14(1H,br),4.32(1H,d,J=

        ?????8.3Hz),4.37(1H,d,J=8.3Hz),4.56(2H,s),4.62

        ?????(1H,br),5.09(1H,s?like),5.21-5.36(3H,m),5.64

        ?????(1H,br?d,J=9.8Hz),5.95(1H,dd,J=15.6Hz,J=

        ?????5.8Hz),6.04-6.16(3H,m),7.25-7.45(10H,m),7.47

        ?????(2H,t,J=7.8Hz),7.60(1H,t?J=7.8Hz),8.10(2H,

        ?????d,J=7.8Hz).

        FAB质谱:968(MH+)。

        本发明实施例33

        9β-9,10-O-(4-苄氧基亚丁基)-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)--2-羟基-3-苯基丙?;?10-脱乙?;?9-二氢浆果赤霉素III

        熔点:102-105℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.25(6H,s),1.40(9H,s),1.60(3H,s),1.64(3H,s),

        ???1.74-1.97(5H,m),2.01-2.43(4H,m),2.30(3H,s),

        ???2.90(1H,d,J=4.4Hz),3.54(2H,t,J=6.3Hz),3.77

        ???(1H,d,J=6.8Hz),4.05-4.18(2H,m),4.33(1H,d,

        ???J=8.3Hz),4.37(1H,d,J=8.3Hz),4.53(2H,s),4.59

        ???-4.70(2H,m),4.88(1H,t,J=5.4Hz),5.10(1H,s

        ???like),5.18(1H,d,J=6.8Hz),5.30(1H,br?d,J=

        ???9.5Hz),5.64(1H,br?d,J=9.5Hz),6.02-6.14(2H,

        ???m),7.22-7.43(10H,m),7.47(2H,t,J=7.8Hz),7.60

        ???(1H,t,J=7.8Hz),8.10(2H,d,J=7.8Hz).

        FAB质谱:970(MH+)。

        本发明实施例34

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?10-脱乙?;?9-二氢-9,10-O-(4-吗啉代亚丁基)浆果赤霉素III

        熔点:128-131℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.25(3H,s),1.40(9H,s),1.53-1.74(2H,m),1.60

        ???(3H,s),1.65(6H,s),1.81-1.93(3H,m),2.03-2.56

        ???(9H,m),2.30(3H,s),2.90(1H,d,J=4.4Hz),3.74

        ???(4H,m),3.78(1H,d,J=6.9Hz),4.05-4.12(1H,br),

        ???4.32(1H,d,J=8.8Hz),4.37(1H,d,J=8.8Hz),4.59

        ???-4.68(2H,m),4.87(1H,t,J=5.3Hz),5.10(1H,s

        ???like),5.18(1H,d,J=6.9Hz),5.28(1H,br?d,J=

        ???9.2Hz),5.63(1H,br?d,J=9.2Hz),6.05(1H,d,J=

        ???4.4Hz),6.08(1H,t,J=8.3Hz),7.23-7.43(5H,m),

        ???7.47(2H,t,J=7.8Hz),7.60(1H,t,J=7.8Hz),8.10

        ???(2H,d,J=7.8Hz).

        FAB质谱:949(MH+)。

        本发明实施例35

        9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?10-脱乙?;?9-二氢-9,10-O-(4-吗啉代亚丁基)浆果赤霉素III

        熔点:127-130℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.27(3H,s),1.41(9H,s),1.54-1.95(m),1.61(3H,

        ???s),1.65(3H,s),1.70(3H,s),2.05-2.26(3H,m),

        ???2.35(3H,s),2.30-2.57(6H,m),2.93(1H,d,J=

        ???5.3Hz),3.74(4H,t,J=4.4Hz),3.81(1H,d,J=

        ???7.4Hz),4.07(1H,br),4.32(1H,d,J=8.3Hz),4.39

        ???(1H,d,J=8.3Hz),4.65(1H,br),4.71(1H,s),4.87

        ???(1H,t,J=5.4Hz),5.10(1H,s?like),5.20(1H,d,J=

        ???7.4Hz),5.32-5.43(2H,m),6.05(1H,d,J=5.3Hz),

        ???6.10(1H,t,J=6.8Hz),6.318(1H,d,J=2.9Hz),6.36

        ???(1H,dd,J=2.9Hz,J=1.9Hz),7.39(1H,d,J=

        ???1.9Hz),7.47(2H,t,J=7.8Hz),7.60(1H,t,J=

        ???7.8Hz),8.11(2H,d,J=7.8H).

        FAB质谱:939(MH+)。

        本发明实施例36

        9β-9,10-O-(2-苄基氨基亚乙基)-4-O-丁?;?13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?4,10二-脱乙?;?9-二氢浆果赤霉素III

        熔点:111-115℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.01(3H,t,J=7.3Hz),1.27(3H,s),1.40(9H,s),

        ???1.58(3H,s),1.63(3H,s),1.70(3H,s),1.74-2.70

        ???(12H,m),2.93(1H,d,J=4.4Hz),2.98(1H,d,J=

        ???4.9Hz),3.85(1H,d,J=7.8Hz),3.89(2H,s),4.07

        ???(1H,s?like),4.31(1H,d,J=8.3Hz),4.38(1H,d,J=

        ???8.3Hz),4.69(1H,d,J=1.9Hz),5.01(1H,t,J=

        ???5.4Hz),5.05(1H,s?like),5.22(1H,d,J=7.8Hz),

        ???5.31(1H,br?d,J=9.8Hz),5.37(1H,br?d,J=9.8Hz),

        ???6.02(1H,d,J=4.4Hz),6.08(1H,br?t,J=7.8Hz),

        ???6.32(1H,d,J=3.4Hz),6.36(1H,dd,J=3.4Hz,J=

        ???1.9Hz),7.20-8.41(6H,m),7.47(2H,t,J=7.3Hz),

        ???7.60(1H,t,J=7.3Hz),8.12(2H,d,J=7.3Hz).

        FAB质谱:959(MH+)。

        本发明实施例37

        9β-4-O-丁?;?13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(呋喃基)-2-羟基丙?;?4,10-二脱乙?;?9-二氢-9,10-O-(2-二甲基氨基亚乙基)浆果赤霉素III

        熔点:125-128℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.01(3H,t,J=6.8Hz),1.28(3H,s),1.40(9H,s),

        ???1.55-1.93(4H,m),1.61(3H,s),1.67(3H,s),1.70

        ???(3H,s),2.10-2.26(3H,m),2.38(6H,s),2.30-2.70

        ???(3H,m),2.71(1H,dd,J=12.8Hz,J=6.0Hz),2.80

        ???(1H,dd,J=12.8Hz,J=3.6Hz),2.93(1H,d,J=

        ???4.9Hz),3.82(1H,d,J=7.3Hz),4.08(1H,br),4.32

        ???(1H,d,J=8.3Hz),4.39(1H,d,J=8.3Hz),4.70(1H,

        ???s),5.01(1H,t?like,J=3.9Hz),5.05(1H,s?like),

        ???5.21(1H,d,J=7.3Hz),5.33(2H,br?s),6.05(1H,d,

        ???J=4.9Hz),6.08(1H,br?t,J=8.0Hz),6.33(1H,d,

        ???J=3.4Hz),6.36(1H,dd,J=3.4Hz,J=1.9Hz),7.39

        ???(1H,d,J=1.9Hz),7.47(2H,t,J=7.3Hz),7.61(1H,

        ???d,J=7.3Hz),8.12(2H,d,J=7.3Hz).

        FAB质谱:897(MH+)。

        本发明实施例38

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?10-脱乙?;?9-二氢-9,10-O-(3-亚丁烯基)浆果赤霉素III1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.26(3H,s),1.40(9H,br),1.43(3H,s),1.62(3H,

        ???s),1.66(3H,s),1.89(1H,s),2.01-2.44(4H,m),

        ???2.30(3H,s),2.58(2H,t,J=6.3Hz),2.91(1H,d,J=

        ???4.4Hz),3.80(1H,d,J=7.3Hz),4.10(1H,br),4.33

        ???(1H,d,J=8.8Hz),4.38(1H,d,J=8.8Hz),4.58-

        ???4.71(2H,m),4.89(1H,t,J=5.3Hz),5.08-5.35(5H,

        ???m),5.63(1H,br?d,J=10.0Hz),5.81-5.93(1H,m),

        ???6.03-6.13(2H,m),7.20-7.53(7H,m),7.60(1H,t,

        ???J=7.3Hz),8.11(2H,d,J=7.3Hz).

        本发明实施例39

        9β-4-O-丁?;?13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-(4-吡啶基)丙?;?4,10-二脱乙?;?9-二氢-9,10-O-异亚丙基浆果赤霉素III

        熔点:108-109℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.03(3H,t,J=6.8Hz),1.24(3H,s),1.40(3H,s),

        ???1.42(9H,s),1.58(3H,s),1.62(3H,s),1.63(3H,s),

        ???1.66(3H,s),1.84(2H,q,J=6.8Hz),2.10-2.37(5H,

        ???m),2.54(2H,m),2.90(1H,d,J=4.4Hz),3.85(1H,

        ???d,J=6.8Hz),4.09(1H,br),4.37(2H,s?like),4.62

        ???(1H,s),4.70(1H,d,J=8.3Hz),5.06(1H,s),5.29

        ???(1H,d,J=8.8Hz),5.51(1H,d,J=6.8Hz),5.52(1H,

        ???d,J=8.8Hz),6.07(2H,br),7.37(2H,d,J=5.4Hz),

        ???7.47(1H,t,J=7.8Hz),7.61(1H,t,J=7.8Hz),8.12

        ???(2H,d,J=7.3Hz),8.60(2H,d,5.9Hz).

        FAB质谱:879(M+)。

        本发明实施例40

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?10-脱乙?;?9-二氢-9,10-O-〔2-(N-噻唑烷并)亚乙基〕浆果赤霉素III

        熔点:114-117℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.26(3H,s),1.40(9H,s),1.57(3H,s),1.62(3H,

        ???br),1.65(3H,s),1.90(1H,s),2.02-2.45(4H,m),

        ???2.32(3H,s),2.75-3.24(7H,m),3.80(1H,d,J=

        ???7.3Hz),4.31(1H,d,J=8.3Hz),4.37(1H,d,J=

        ???8.3Hz),4.60-4.70(2H,m),5.05(1H,t,J=4.3Hz),

        ???5.10(1H,s),5.23(1H,d,J=6.8Hz),5.29(1H,d,J=

        ???9.0Hz),5.62(1H,d,J=9.0Hz),6.00-6.14(2H,m),

        ???7.24-7.46(5H,m),7.47(2H,t,J=7.8Hz),7.60(1H,

        ???t,J=7.8Hz),8.10(2H,d,J=7.8Hz).

        FAB质谱:923(MH+)。

        本发明实施例41

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?10-脱乙?;?9-二氢-9,10-O-〔2-(4-吡啶基甲基氨基)亚乙基〕浆果赤霉素III

        熔点:138-141℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.26(3H,s),1.40(9H,s),1.58(3H,s),1.63(6H,s),

        ???1.90(1H,s),2.01-2.43(4H,m),2.30(3H,s),2.89

        ???(1H,d,J=4.9Hz),2.99(1H,d,J=4.9Hz),3.82(1H,

        ???d,J=7.3Hz),3.91(1H,s),4.08(1H,br),4.31(1H,

        ???d,J=8.8Hz),4.38(1H,d,J=8.8Hz),4.58-4.74

        ???(2H,m),5.00(1H,t,J=4.9Hz),5.10(1H,s),5.23

        ???(1H,d,J=7.3Hz),5.28(1H,d,J=9.7Hz),5.61(1H,

        ???d,J=9.7HZ),6.03(1H,d,J=4.9Hz),6.10(1H,t,

        ???J=7.9Hz),7.21-7.51(9H,m),7.61(1H,t,J=

        ???7.4Hz),8.10(2H,d,J=7.4Hz),8.56(2H,d,J=

        ???5.9Hz).

        FAB质谱:942(MH+)。

        本发明实施例42

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?10-脱乙?;?9-二氢-9,10-O-〔2-(2-吗啉代乙基氨基)亚乙基〕浆果赤霉素III????

        熔点:124-127℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.26(3H,s),1.40(9H,s),1.57(3H,s),1.60(3H,s),

        ???1.65(3H,s),2.02-2.60(12H,m),2.30(3H,s),2.75

        ???-2.87(2H,m),2.90(2H,d,J=4.9Hz),2.99(1H,d,

        ???J=4.9Hz),3.72(4H,t,J=4.4Hz),3.81(1H,d,J=

        ???7.3Hz),4.08(1H,s),4.32(1H,d,J=8.3Hz),4.37

        ???(1H,d,J=8.3Hz),4.62(1H,s),4.98(1H,t,J=

        ???4.9Hz),5.10(1H,s),5.22(1H,d,J=7.3Hz),5.29

        ???(1H,br?d,J=9.3Hz),5.62(1H,br?d,J=9.3Hz),6.04

        ???(1H,d,J=4.9Hz),6.09(1H,t,J=7.3Hz),7.18-

        ???7.52(7H,m),7.60(1H,t,J=7.4Hz),8.10(2H,d,J=

        ???7.4Hz).

        FAB质谱:964(MH+)。

        本发明实施例43

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?9,10-O-〔2-(环丙基氨基)亚乙基〕-10-脱乙?;?9-二氢浆果赤霉素III

        熔点:139-142℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.35-0.54(4H,m),1.26(3H,s),1.40(9H,s),1.57

        ???(3H,s),1.61(3H,s),1.68(3H,s),1.89(1H,br),

        ???2.02-2.44(5H,m),2.30(3H,s),2.90(1H,d,J=

        ???4.9Hz),3.05(2H,d,J=5.3Hz),3.80(1H,d,J=

        ???7.4Hz),4.10(1H,s),4.32(1H,d,J=8.3Hz),4.38

        ???(1H,d,J=8.3Hz),4.62(1H,s),4.96(1H,t,J=

        ???5.3Hz),5.10(1H,s),5.21(1H,d,J=7.4Hz),5.29

        ???(1H,br?d,J=8.8Hz),5.62(1H,br?d,J=8.8Hz),6.00

        ???-6.12(2H,m),7.19-7.52(5H,m)7.60(1H,t,J=

        ???7.8Hz),8.10(2H,d,J=7.8Hz).

        FAB质谱:891(MH+)。

        本发明实施例44

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?10-脱乙?;?9,10-O-〔2-(二乙基氨基)亚乙基〕-9-二氢浆果赤霉素III

        熔点:132-135℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.08(6H,t,J=7.3Hz),1.25(3H,s),1.40(9H,s),

        ???1.60(3H,s),1.62(3H,s),1.67(3H,s),1.88(1H,s),

        ???1.99-2.43(4H,m),2.29(3H,s),2.60-2.73(4H,m),

        ???2.80-2.93(2H,m),2.89(1H,d,J=4.9Hz),3.77(1H,

        ???d,J=6.8Hz),4.10(1H,br),4.32(1H,d,J=8.8Hz),

        ???4.37(1H,d,J=8.8Hz),4.58-4.69(2H,m),4.97(1H,

        ???br),5.10(1H,s),5.20(1H,d,J=6.8Hz),5.29(1H,

        ???d,J=8.8Hz),5.62(1H,d,J=8.8Hz),6.01-6.12

        ???(2H,m),7.24-7.52(7H,m),7.60(1H,t,J=7.3Hz),

        ???8.10(2H,d,J=7.3Hz).

        FAB质谱:907(MH+)。

        本发明实施例45

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?10-脱乙?;?9-二氢-9,10-O-〔2-(2-羟基乙基氨基)亚乙基〕浆果赤霉素III

        熔点:149-151℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.26(3H,s),1.40(9H,s),1.57(3H,s),1.60(3H,s),

        ???1.64(3H,s),1.89-2.47(m),2.30(3H,s),2.83-

        ???2.96(3H,m),3.00(2H,d,J=4.9Hz),3.67(2H,t,J=

        ???4.9Hz),3.81(1H,d,J=7.3Hz),4.08(1H,s),4.31

        ???(1H,d,J=8.8Hz),4.37(1H,d,J=8.8Hz),4.62(1H,

        ???s),4.97(1H,t,J=4.9Hz),5.10(1H,s),5.22(1H,d,

        ???J=7.3Hz),5.28(1H,d,J=9.8Hz),5.64(1H,d,J=

        ???9.8Hz),6.04(1H,d,J=4.9Hz),7.21-7.51(7H,m),

        ???7.60(1H,t,J=7.3Hz),8.10(2H,d,J=7.3Hz).

        FAB质谱:895(MH+)。

        本发明实施例46

        9β-9,10-O-〔2-(N-氮杂环丙?;?亚乙基〕-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?10-脱乙?;?9-二氢浆果赤霉素III?1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ????1.35(3H,s),1.42(9H,s),1.53(3H,s),1.68(3H,s),

        ????1.78(3H,s),1.70-2.00(2H,m),2.12-2.48(6H,m),

        ????2.42(3H,s),2.48-2.58(1H,m),2.64-2.73(1H,m),

        ???2.96(1H,d,J=4.5Hz),3.86(1H,d,J=7.0Hz),4.03

        ???-4.11(1H,m),4.31(1H,d,J=8.3Hz),4.41(1H,d,J

        ???=8.3Hz),4.65(1H,d,J=8.5Hz),5.03-5.32(4H,m),

        ???5.40-5.55(2H,m),6.01(1H,d,J=4.5Hz),6.14-

        ???6.25(2H,m),7.20-7.45(5H,m),7.49(2H,t,J=

        ???7.5Hz),7.60(1H,t,J=7.5Hz),8.14(2H,d,J=

        ???7.5Hz).

        FAB质谱:859(MH+-H2O)。

        本发明实施例47

        9β-13-O-〔3-(叔丁氧基羰基氨基)-2-羟基-2-甲基-3-(4-吡啶基)丙?;?10-脱乙?;?9-二氢-9,10-O-(异亚丙基)浆果赤霉素III

        熔点:170-174℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.30(s),1.37(9H,s),1.40(s),1.43(s),1.58(s),

        ???1.63(s),1.68(s),2.05(1H,m),2.09(1H,m),2.21

        ???(1H,m),2.25(1H,m),2.47(3H,s),2.90(1H,d,J=

        ???4Hz),3.77(1H,d,J=7Hz),4.08(1H,br),4.32(1H,

        ???br),4.38(2H,s),4.69(1H,d,J=8.5Hz),5.00(1H,

        ???d,J=10Hz),5.11(1H,br),5.48(1H,d,J=7Hz),

        ???5.78(1H,d,J=10Hz),6.05(1H,d,J=4Hz),6.23

        ???(1H,t),7.36(2H,s-d),7.48(2H,t,J=7.5Hz),7.61

        ???(1H,t,J=7.5Hz),8.12(2H,d,J=7.5Hz),8.59(2H,

        ???s-d).

        FAB质谱:865(MH+)。

        本发明实施例48

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-(4-吡啶基)丙?;?4,10-二脱乙?;?9-二氢-9,10-O-异亚丙基-4-O丙?;嗝顾豂II

        熔点:140-147℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDC13/TMS)δ(ppm)

        ???1.25(3H,s),1.33(3H,t,J=7.8Hz),1.41(9H,s),

        ???1.42(3H,s),1.53(3H,s),1.63(3H,s),1.66(6H,s),

        ???2.07-2.36(4H,m),2.40-2.57(2H,m),2.91(1H,d,

        ???J=4.9Hz),3.80(1H,d,J=7.3Hz),4.08(1H,br),

        ???4.38(2H,ABq,J=15.6Hz),4.62(1H,s),4.72(1H,d,

        ???J=7.9Hz),5.04(1H,s),5.28(1H,d,J=8.5Hz),5.52

        ???(1H,d,J=7.3Hz),5.70(1H,d,J=8.5Hz),6.07(2H,

        ???br),7.36(2H,s),7.47(2H,t,J=7.8Hz),7.61(1H,

        ???t,J=7.3Hz),8.13(2H,d,J=7.3Hz),8.60(2H,br).

        FAB质谱:865(MH+)。

        本发明实施例49

        9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?4-O-环丙烷羰基-4,10-二脱乙?;?9-二氢-9,10-O-(2-亚丙烯基)浆果赤霉素III

        熔点:225-228℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.04-1.16(2H,m),1.27(3H,s),1.41(9H,s),1.60

        ???(3H,s),1.60-1.75(2H,m),1.68(3H,s),1.74(3H,

        ???s),1.92(1H,s),2.03-2.32(3H,m),2.41(1H,dd,J

        ???=14.0Hz,J=9.6Hz),2.92(1H,d,J=4.4Hz),3.88

        ???(1H,d,J=7.3Hz),3.96-4.14(2H,m),4.27(1H,d,J

        ???=8.8Hz),4.33(1H,d,J=8.8Hz),4.56(1H,d,J=

        ???7.8Hz),4.71(1H,s?like),5.05(1H,s?like),5.22(1H,

        ???d,J=5.8Hz),5.28(1H,d,J=7.3Hz),5.37(2H,s

        ???like),5.45(1H,d,J=10.3Hz),5.56(1H,d,J=

        ???17.1Hz),5.97-6.15(3H,m),6.27-6.40(2H,m),7.36

        ???(1H,s?like),7.48(2H,t,J=7.8Hz),7.60(1H,t,J=

        ???7.8Hz),8.05(2H,d,J=7.8Hz).

        FAB质谱:864(MH+)。

        本发明实施例50

        9β-9,10-O-(2-氨基亚乙基)-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?10-脱乙?;?9-二氢浆果赤霉素III

        熔点:155-158℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.26(3H,s),1.40(9H,s),1.58(3H,s),1.60(3H,s),

        ???1.65(3H,s),2.00-2.44?4H,m),2.30(3H,s),2.90

        ???(1H,d,J=4.9Hz),3.02(2H,d,J=4.4Hz),3.82(1H,

        ???d,J=7.4Hz),4.09(1H,s?like),4.32(1H,d,J=

        ???8.3Hz),4.37(1H,d,J=8.3Hz),4.62(1H,s?like),

        ???4.84(1H,t,J=4.9Hz),5.10(1H,s),5.23(1H,d,J=

        ???7.4Hz),5.28(1H,d,J=9.2Hz),5.62(1H,d,J=

        ???9.2Hz),6.04(1H,d,J=4.9Hz),6.08(1H,t,J=

        ???8.3Hz),7.20-7.56(7H,m),7.47(1H,t,J=7.8Hz),

        ???8.10(2H,d,J=7.8Hz).

        FAB质谱:851(MH+)。

        本发明实施例51

        9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?4-O-环丙烷羰基-4,10-二脱乙?;?9-二氢-9,10-O-(2-吗啉代亚乙基)浆果赤霉素III

        熔点:147-148℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.01-1.19(2H,m),1.27(3H,s),1.41(9H,s),1.58

        ???(3H,s),1.65(3H,s),1.72(3H,s),1.92(1H,s),2.04

        ???-2.32(3H,m),2.40(1H,dd,J=15.1Hz,J=9.2Hz),

        ???2.52-2.70(4H,m),2.74(1H,dd,J=13.1Hz,J=

        ???4.8Hz),2.90(1H,d,J=4.9Hz),3.73(4H,t?like,J=

        ???4.9Hz),3.81(1H,d,J=6.8Hz),4.06(1H,br),4.26

        ???(1H,d,J=8.8Hz),4.33(1H,d,J=8.8Hz),4.66(1H,

        ???d,J=8.3Hz),4.71(1H,s),4.89-5.09(2H,m),5.21

        ???(1H,d,J=7.4Hz),5.37(2H,m),6.01-6.10(2H,m),

        ???6.29-6.39(2H,m),7.36(1H,s?like),7.48(2H,t,

        ???J=7.8Hz),7.60(1H,t,J=7.8Hz),8.05(2H,d,J=

        ???7.8Hz).

        FAB质谱:937(MH+)。

        本发明实施例52

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?4-O-环丙烷羰基-4,10-二脱乙?;?9-二氢-9,10-O-(2-亚丙烯基)浆果赤霉素III

        熔点:218-220℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.00-1.10(2H,m),1.20-1.45(2H,m),1.25(3H,s),

        ???1.40(3H,s),1.50-1.80(2H,m),1.58(3H,s),1.95

        ???(1H,s),2.07-2.24(3H,m),2.41(1H,dd,J=15.1Hz,

        ???J=9.8Hz),2.88(1H,d,J=3.9Hz),3.86(1H,d,J=

        ???6.9Hz),4.08(1H,br),4.26(1H,d,J=8.7Hz),4.31

        ???(1H,d,J=8.7Hz),4.53(1H,br?d,J=7.9Hz),5.04

        ???(1H,s),5.21(1H,d,J=6.3Hz),5.25-5.33(2H,m),

        ???5.44(1H,d,J=10.7Hz),5.56(11H,d,J=17.0Hz),

        ???5.609(1H,d,J=8.8Hz),5.96-6.12(3H,m),7.24-

        ???7.51(7H,m),7.60(1H,t,J=7.3Hz),7.60(1H,t,J=

        ???7.3Hz),8.03(2H,d,J=7.3Hz).

        FAB质谱:874(MH+)。

        本发明实施例53

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?4-O-环丙烷羰基-4,10-二脱乙?;?9-二氢-9,10-O-(2-吗啉代亚乙基)浆果赤霉素III

        熔点:146-147℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.96-1.02(2H,m),1.24(3H,s),1.18-1.40(2H,m),

        ???1.40(9H,s),1.57(6H,s),1.64(3H,s),1.90-2.15

        ???(4H,m),2.30-2.98(8H,m),3.61-3.83(5H,m),4.06

        ???(1H,br),4.26(1H,d,J=8.3Hz),4.31(1H,d,J=

        ???8.3Hz),4.50-4.74(2H,m),4.92-5.03(2H,m),5.20

        ???(1H,d,J=6.4Hz),5.27(1H,d,J=9.3Hz),5.68(1H,

        ???d,J=9.3Hz),5.89-6.15(2H,m),7.17-7.52(7H,

        ???m),7.60(1H,t,J=7.3Hz),8.03(2H,d,J=7.3Hz).

        FAB质谱:947(MH+)。

        本发明实施例54

        9β-13-O-〔3-(叔丁氧基羰基氨基)-2-羟基-2-甲基-3-(4-吡啶基)丙?;?4-O-丁?;?4,10-二脱乙?;?9-二氢-9,10-O-异亚丙基浆果赤霉素III

        熔点:160-163℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.11(3H,t,J=7.5Hz),1.29(s),1.37(9H,s),1.40

        ???(s),1.42(s),1.58(s),1.64(s),1.67(s),1.92(1H,

        ???m),2.07(2H,m),2.24(2H,m),2.56(1H,m),2.71(1H,

        ???m),2.92(1H,s-d),3.77(1H,d,J=7Hz),4.08(1H,

        ???br),4.30(1H,br),4.38(2H,s),4.71(1H,d,J=

        ???8Hz),5.00(1H,d,J=10Hz),5.06(1H,br),5.48(1H,

        ???d,J=7Hz),5.80(1H,d,J=10Hz),6.06(1H,s-d),

        ???6.20(1H,t-br),7.37(2H,d,J=5Hz),7.48(2H,t,

        ???J=7.5Hz),7.61(1H,t,J=7.5Hz),8.14(2H,d,J=

        ???7.5Hz),8.59(2H,d,J=5Hz).

        FAB质谱:893(M+)。

        本发明实施例55

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-(4-吡啶基)丙?;?4-O-环丙烷羰基-4,10-二脱乙?;?9-二氢-9,10-O-异亚丙基浆果赤霉素III

        熔点:128-134℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.23(3H,s),1.26(4H,s),1.41(3H,s),1.42(3H,s),

        ???1.48(9H,s),1.53(3H,s),1.60(3H,s),1.66(3H,s),

        ???1.92-2.37(5H,m),2.88(1H,d,J=5.3Hz),3.76(1H,

        ???d,J=7.3Hz),4.06(1H,m),4.30(2H,s),4.60(1H,

        ???br),4.68(1H,d,J=8.3Hz),5.06(1H,s),5.27(1H,

        ???d,J=8.0Hz),5.54(1H,d,J=7.3Hz),5.89(1H,d,

        ???J=8.0Hz),6.01(1H,t,J=7.3Hz),6.08(1H,d,J=

        ???5.3Hz),7.37(2H,br),7.48(2H,t,J=7.8Hz),7.61

        ???(1H,t,J=7.3Hz),8.03(2H,d,J=7.3Hz),8.59(2H,

        ???br).

        FAB质谱:877(MH+)。

        本发明实施例56

        9β-13-O-〔3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基-2-甲基丙?;?4-O-环丙烷羰基-4,10-二脱乙?;?9-二氢-9,10-O-(2-亚丙烯基)浆果赤霉素III

        熔点:230-233℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.20-1.80(4H,m),1.31(3H,s),1.37(9H,s),1.45

        ???(3H,s),1.60(3H,s),1.69(3H,s),1.89-2.02(2H,

        ???m),2.92(1H,d,J=3.9Hz),3.86(1H,d,J=7.3Hz),

        ???4.05-4.13(1H,m),4.22(1H,br?s),4.29(1H,d,J=

        ???8.3Hz),4.33(1H,d,J=8.3Hz),4.61(1H,d,J=

        ???7.9Hz),5.07(1H,s?like),5.16-5.29(3H,m),5.44

        ???(1H,d,J=10.8Hz),5.50(1H,d,J=9.7Hz),5.56(1H,

        ???d,J=17.1Hz),5.98-6.10(1H,m),6.08(1H,d,J=

        ???3.9Hz),6.20(1H,t,J=8.0Hz),6.30(1H,d,J=

        ???3.5Hz),6.35(1H,m),7.36(1H,s?like),7.49(2H,t,

        ???J=7.4Hz),7.61(1H,t,J=7.4Hz),8.06(2H,d,J=

        ???7.4Hz).

        FAB质谱:878(MH+)。

        本发明实施例57

        9β-13-O-〔3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基-2-甲基丙?;?4-O-环丙烷羰基-4,10-二脱乙?;?9-二氢-9,10-O-(2-吗啉代亚乙基)浆果赤霉素III

        熔点:140-143℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.10-1.82(4H,m),1.31(3H,s),1.37(9H,s),1.58

        ???(3H,s),1.66(6H,s),1.67(3H,s),1.90-2.03(1H,

        ???m),1.92(1H,s),2.04-2.36(4H,m),2.50-2.70(4H,

        ???m),2.74(1H,dd,J=13.6Hz,J=5.3Hz),2.82(1H,dd,

        ???J=13.6Hz,J=3.4Hz),2.90(1H,d,J=3.9Hz),3.73

        ???(4H,t,J=4.8Hz),3.78(1H,d,J=7.3Hz),4.02-

        ???4.10(1H,m),4.18(1H,br),4.28(1H,d,J=8.8Hz),

        ???4.34(1H,d,J=8.8Hz),4.69(1H,d,J=8.3Hz),5.02

        ???(1H,t,J=4.9Hz),5.07(1H,s),5.15-5.26(2H,m),

        ???5.48(1H,d,J=9.8Hz),6.06(1H,d,J=3.9Hz),6.19

        ???(1H,t,J=8.3Hz),6.30(1H,d,J=3.0Hz),6.35(1H,

        ???dd,J=3.0Hz,J=2.9Hz),7.36(1H,d,J=2.9Hz),

        ???7.49(2H,t,J=7.8Hz),7.61(1H,t,J=7.8Hz),8.06

        ???(2H,d,J=7.8Hz).

        FAB质谱:951(MH+)。

        本发明实施例58

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-(4-吡啶基)丙?;?4-O-环丙烷羰基-4,10-二脱乙?;?9-二氢-9,10-O-(2-亚丙烯基)浆果赤霉素III

        熔点:156-157℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.04-1.16(2H,m),1.20-1.80(2H,m),1.23(3H,s),

        ???1.41(9H,s),1.63(6H,s),1.67(3H,s),1.95-2.28

        ???(4H,m),2.36-2.47(1H,m),2.87(1H,d,J=4.4Hz),

        ???3.85(1H,d,J=7.2Hz),4.08(1H,br),4.27(1H,d,

        ???J=8.8Hz),4.30(1H,d,J=8.8Hz),4.47-4.65(2H,

        ???m),5.05(1H,s?like),5.21(1H,d,J=5.8Hz),5.23-

        ???5.34(2H,m),5.45(1H,d,J=10.3Hz),5.56(1H,d,

        ???J=17.2Hz),5.79(1H,d,J=9.8Hz),6.00-6.12(3H,

        ???m),7.35(2H,d,J=5.8Hz),7.47(2H,t,J=7.8Hz),

        ???7.60(1H,t,J=7.8Hz),8.02(2H,d,J=7.8Hz),8.57

        ???(2H,d,J=5.8Hz).

        FAB质谱:875(MH+)。

        本发明实施例59

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-(4-吡啶基)丙?;?10-脱乙?;?7-脱氧-9-二氢-9,10-O-异亚丙基浆果赤霉素III

        熔点:162.5-167.5℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.23(3H,s),1.43(9H,s),1.51(3H,s),1.55(3H,s),

        ???1.57(3H,s),1.61(3H,s),1.71(3H,s),1.60-2.10

        ???(5H,m),1.97(1H,s),2.28(3H,s),2.34(1H,dd,J=

        ???10.2,15.1Hz),2.91(1H,d,J=4.9Hz),4.12(1H,d,

        ???J=7.1Hz),4.27(1H,d,J=8.3Hz),4.32(1H,d,J=

        ???8.3Hz),4.63(1H,br?s),4.82(1H,br?s),4.93(1H,br

        ???s),5.30(1H,d,J=9.1Hz),5.56(1H,d,J=7.1Hz),

        ???5.81(1H,d,J=9.1Hz),6.00(1H,d,J=4.9Hz),6.09

        ???(1H,br?t,J=7.8Hz),7.36(2H,d,J=5.9Hz),7.47

        ???(2H,t,J=7.3Hz),7.60(1H,t,J=7.3Hz),8.12(2H,

        ???d,J=7.3Hz),8.59(2H,d,J=5.9Hz)

        本发明实施例60

        9β-13-O-〔3-(叔丁氧基羰基氨基)-2-羟基-2-甲基-3-(4-吡啶基)丙?;?4-O-环丙烷羰基-4,10-二脱乙?;?9-二氢-9,10-O-异亚丙基浆果赤霉素III

        熔点:152-158℃(由二噁烷冷冻干燥)?1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.16(4H,m),1.28(3H,s),1.39(9H,s),1.40(3H,s),

        ???1.42(3H,s),1.58(3H,s),1.60(3H,s),1.67(3H,s),

        ???1.83-2.36(5H,m),2.89(1H,d,J=3.9Hz),3.74(1H,

        ???d,J=7.3Hz),4.07(1H,m),4.32(2H,s),4.70(1H,d,

        ???J=8.3Hz),5.00(1H,d,J=10.3Hz),5.07(1H,s),

        ???5.49(1H,d,J=6.8Hz),5.87(1H,d,J=9.8Hz),6.08

        ???(1H,d,J=4.4Hz),6.20(1H,m),7.38(2H,d,J=

        ???5.9Hz),7.49(2H,t,J=7.8Hz),7.62(1H,t,J=

        ???7.3Hz),8.04(2H,d,J=7.3Hz),8.57(2H,d,J=

        ???5.4Hz).

        FAB质谱:891(MH+)。

        本发明实施例61

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?4-O-环丙烷羰基-4,10-二脱乙?;?7-脱氧-9-二氢-9,10-O-(2-亚丙烯基)浆果赤霉素III

        熔点:130-133℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.00-1.10(2H,m),1.20-1.40(2H,m),1.24(3H,s),

        ???1.41(9H,s),1.45(3H,s),1.62(3H,s),1.62-2.10

        ???(6H,m),2.01(3H,s),2.38(1H,dd,J=14.7Hz,J=

        ???8.8Hz),2.89(1H,d,J=4.4Hz),4.14(1H,d,J=

        ???7.0Hz),4.18(1H,d,J=8.8Hz),4.27(1H,d,J=

        ???8.8Hz),4.60(1H,br?s),4.65(1H,br?s),4.87(1H,s),

        ???5.23(1H,d,J=5.9Hz),5.20-5.20(1H,m),5.29(1H,

        ???d,J=5.9Hz),5.46(1H,d,J=10.7Hz),5.57(1H,d,

        ???J=17.6Hz),5.74(1H,d,J=9.8Hz),5.95-6.08(3H,

        ???m),7.29(1H,d,J=7.3Hz),7.34(2H,t,J=7.3Hz),

        ???7.42(2H,d,J=7.3Hz),7.47(2H,t,J=7.3Hz),7.60

        ???(1H,t,J=7.3Hz),8.04(2H,d,J=7.3Hz).

        FAB质谱:858(MH+)。

        本发明实施例62

        9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?4-O-环丙烷羰基-4,10-二脱乙?;?7-脱氧-9-二氢-9,10-O-(2-亚丙烯基)浆果赤霉素III

        熔点:132-135℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.03-1.13(2H,m),1.25(3H,s),1.30-1.50(2H,m),

        ???1.41(9H,s),1.46(3H,s),1.63(3H,s),1.71-1.95

        ???(5H,m),1.78(3H,br?s),2.01-2.21(2H,m),2.40

        ???(1H,dd,J=15.1Hz,J=9.8Hz),2.91(1H,d,J=

        ???4.9Hz),4.14-4.22(2H,m),4.29(1H,d,J=8.3Hz),

        ???4.33(1H,br?s),4.71(1H,s),4.87(1H,s),5.24(1H,

        ???d,J=6.3Hz),5.31(1H,d,J=6.8Hz),5.37(1H,br?d,

        ???J=9.8Hz),5.44(1H,br?d,J=9.8Hz),5.46(1H,d,

        ???J=10.8Hz),5.57(1H,d,J=17.1Hz),5.93-6.10(3H,

        ???m),6.31(1H,d,J=2.9Hz),6.34(1H,dd,J=2.9Hz,

        ???J=1.9Hz),7.36(1H,s?like),7.48(2H,t,J=7.4Hz),

        ???7.61(1H,t,J=7.43Hz),8.06(2H,d,J=7.4Hz).

        FAB质谱:848(MH+)。

        本发明实施例63

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?4-O-环丙烷羰基-4,10-二脱乙?;?7-脱氧-9-二氢-9,10-O-(2-吗啉代亚乙基)浆果赤霉素III

        熔点:118-121℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.00-1.09(2H,m),1.24(3H,s),1.20-1.40(2H,m),

        ???1.40(9H,s),1.43(3H,s),1.50-2.21(6H,m),1.55-

        ???1.62(6H,m),2.39(1H,dd,J=14.5Hz,J=10.2Hz),

        ???2.53-2.82(5H,m),2.86(1H,D,J=3.9Hz),3.74(4H,

        ???t,J=4.9Hz),4.08(1H,d,J=7.3Hz),4.18(1H,d,

        ???J=8.8Hz),4.26(1H,d,J=8.8Hz),4.61(1H,br),

        ???4.86(1H,br?s),5.04(1H,dd,J=4.4Hz,J=3.4Hz),

        ???5.23(1H,d,J=7.3Hz),5.29(1H,d,J=8.3Hz),5.73

        ???(1H,d,J=8.3Hz),5.95-6.06(2H,m),7.21-7.30

        ???(1H,),7.41(2H,d,J=7.3Hz),7.47(2H,t,J=

        ???7.3Hz),7.60(1H,t,J=7.3Hz),8.04(2H,d,J=

        ???7.3Hz).

        FAB质谱:931(MH+)。

        本发明实施例64

        9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?4-O-环丙烷羰基-4,10-二脱乙?;?7-脱氧-9-二氢-9,10-O-(2-吗啉代亚乙基)浆果赤霉素III

        熔点:129-132℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.02-1.12(2H,m),1.26(3H,s),1.34-1.49(2H,m),

        ???1.41(9H,s),1.60(6H,s),1.70-2.21(6H,m),1.76

        ???(3H,s),2.39(1H,dd,J=15.2Hz,J=9.7Hz),2.53-

        ???2.82(6H,m),2.90(1H,d,J=4.8Hz),3.74(4H,t,J=

        ???4.4Hz),4.11(1H,d,J=7.3Hz),4.18(1H,d,J=

        ???8.8Hz),4.29(1H,d,J=8.8Hz),4.71(1H,s),4,86

        ???(1H,br?s),5.04(1H,t?like,J=5.4Hz),5.24(1H,d,

        ???J=7.3Hz),5.37(1H,d,J=8.8Hz),5.44(1H,d,J=

        ???8.8Hz),5.98-6.09(2H,m),6.31(1H,d,J=2.9Hz),

        ???6.34(1H,dd,J=2.9Hz,J=1.4Hz),7.36(1H,d,J=

        ???1.4Hz),7.48(2H,t,J=7.8Hz),7.61(1H,t,J=

        ???7.8Hz),8.06(2H,d,J=7.8Hz).

        FAB质谱:921(MH+)。

        本发明实施例65

        9β-13-O-〔3-(叔丁氧基羰基氨基)-2-羟基-2-甲基-3-(4-吡啶基)丙?;?4-O-环丙烷羰基-4,10-二脱乙?;?7-脱氧-9-二氢-9,10-O-异亚丙基浆果赤霉素III

        熔点:160-163℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.00-2.30(11H,m),1.26(3H,s),1.38(9H,s),1.42

        ???(3H,s),1.46(6H,s),1.56(3H,s),1.61(6H,s),2.91

        ???(1H,d,J=4.0Hz),4.10(1H,d,J=7.3Hz),4.22(1H,

        ???d,J=8.8Hz),4.27(1H,d,J=8.8Hz),4.80-4.90

        ???(2H,m),5.00(1H,d,J=9.8Hz),5.52(1H,d,J=

        ???7.3Hz),5.90(1H,d,J=9.8Hz),6.01(1H,d,J=

        ???4.0Hz),6.15-6.25(1H,m),7.36(2H,d,J=5.3Hz),

        ???7.48(2H,t,J=7.3Hz),7.61(1H,t,J=7.3Hz),8.05

        ???(2H,d,J=7.3Hz),8.56(2H,d,J=5.3Hz).

        FAB质谱:875(MH+)。

        本发明实施例66

        9β-13-O-〔3-(叔丁氧基羰基氨基)-2-羟基-2-甲基-3-(2-吡啶基)丙?;?4-O-环丙烷羰基-4,10-二脱乙?;?9-二氢-9,10-O-异亚丙基浆果赤霉素III

        熔点:151-153℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.15(4H,m),1.30(3H,s),1.39(3H,s),1.42(9H,s),

        ???1.51(3H,s),1.57(6H,s),1.63(3H,s),1.66(3H,s),

        ???2.09-2.42(5H,m),2.92(1H,d,J=4.9Hz),3.82(1H,

        ???m),4.04(1H,m),4.34(2H,ABq,J=7.8Hz),4.76(1H,

        ???d,J=8.3Hz),5.10(1H,s),5.11(1H,d,J=10.3Hz),

        ???5.48(1H,d,J=7.3Hz),6.04(1H,d,J=4.9Hz),6.16

        ???(1H,t,J=8.3Hz),7.23(1H,t,J=4.4Hz),7.42(1H,

        ???d,J=7.8Hz),7.49(2H,t,J=7.8Hz),7.61(1H,t,

        ???J=7.3Hz),7.72(1H,t,J=6.8Hz),8.07(2H,d,J=

        ???7.3Hz),8.46(1H,d,J=4.4Hz).

        FAB质谱:891(MH+)。

        本发明实施例67

        9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?10-脱乙?;?7-脱氧-9,10-O-亚乙基-9-二氢浆果赤霉素III

        熔点:104-106℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.20-2.10(5H,m),1.25(3H,s),1.42(9H,s),1.49

        ???(3H,d,J=4.8Hz),1.50(3H,s),1.62(3H,s),1.74

        ???(3H,s),2.30-2.50(1H,m),2.32(3H,s),2.93(1H,d,

        ???J=4.8Hz),4.12(1H,d,J=7.4Hz),4.24(1H,d,J=

        ???8.8Hz),4.29(1H,br),4.33(1H,d,J=8.8Hz),4.72

        ???(1H,d,J=2.0Hz),4.92(1H,s),5.06(1H,q,J=

        ???4.8Hz),5.25(1H,d,J=8.3Hz),5.39(1H,d,J=

        ???10.0Hz),5.44(1H,d,J=10.0Hz),6.01(1H,d,J=

        ???4.8Hz),6.05-6.20(1H,m),6.31(1H,d,J=2.9Hz),

        ???6.35(1H,dd,J=2.9Hz,J=1.9Hz),7.22(1H,s?like),

        ???7.47(2H,t,J=7.8Hz),7.59(1H,t,J=7.8Hz),8.13

        ???(2H,d,J=7.8Hz).

        FAB质谱:810(MH+)。

        本发明实施例68

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?10-脱乙?;?7-脱氧-9-二氢-9,10-O-(2-亚丙烯基)浆果赤霉素III

        熔点:140-143℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.20-2.20(5H,m),1.25(3H,s),1.41(9H,s),1.48

        ???(3H,s),1.63(3H,s),2.27(3H,s),2.37(1H,dd,J=

        ???15.1Hz,J=5.3Hz),2.90(1H,d,J=4.4Hz),4.15(1H,

        ???d,J=7.3Hz),4.23(1H,d,J=8.3Hz),4.31(1H,d,

        ???J=8.3Hz),4.50(1H,s?like),4.62(1H,s?like),4.91

        ???(1H,s),5.20-5.40(2H,m),5.23(1H,d,J=5.9Hz),

        ???5.46(1H,d,J=10.2Hz),5.57(1H,d,J=17.6Hz),

        ???5.71(1H,d,J=9.8Hz),5.90-6.20(3H,m),7.20-

        ???7.50(7H,m),7.60(1H,t,J=7.9Hz),8.11(2H,d,J=

        ???7.9Hz).

        FAB质谱:832(MH+)。

        本发明实施例69

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-(2-吡啶基)丙?;?4-O-环丙烷羰基-4,10-二脱乙?;?9-二氢-9,10-O-异亚丙基浆果赤霉素III

        熔点:138-141℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.23-1.29(4H,m),1.27(3H,s),1.39(9H,s),1.41

        ???(3H,s),1.58(3H,s),1.63(3H,s),1.66(3H,s),1.74

        ???(3H,s),1.85(1H,s),1.98-2.39(5H,m),2.94(1H,

        ???d,J=4.9Hz),3.84(1H,d,J=7.3Hz),4.06(1H,m),

        ???4.30(2H,ABq,J=8.3Hz),4.55(1H,br),4.79(1H,d,

        ???J=8.3Hz),4.88(1H,s),5.07(1H,s),5.34(1H,d,

        ???J=9.3Hz),5.55(1H,d,J=6.8Hz),5.83(1H,d,J=

        ???9.8Hz),6.05(2H,m),7.22(1H,dd,J=7.3Hz,4.9Hz),

        ???7.41(1H,d,J=7.8Hz),7.47(2H,t,J=7.8Hz),7.60

        ???(1H,t,J=7.3Hz),7.71(1H,t,J=6.4Hz),8.05(2H,

        ???d,J=6.8Hz),8.50(1H,d,J=4.4Hz).

        FAB质谱:877(MH+)。?

        本发明实施例70

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-(4-吡啶基)丙?;?4-O-环丙烷羰基-4,10-二脱乙?;?7-脱氧9-二氢-9,10-O-异亚丙基浆果赤霉素III

        熔点:155-157℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.00-1.20(2H,m),1.20-1.50(2H,m),1.22(3H,s),

        ???1.43(9H,s),1.47(3H,s),1.50-2.10(6H,m),1.56

        ???(6H,s),1.60(6H,s),2.35(1H,t?like,J=10.8Hz),

        ???2.87(1H,d,J=4.4Hz),4.11(1H,d,J=7.4Hz),4.20

        ???(1H,d,J=8.8Hz),4.27(1H,d,J=8,8Hz),4.59(1H,

        ???s),4.87(1H,s),5.28(1H,d,J=8.8Hz),5.56(1H,d,

        ???J=7.4Hz),5.84(1H,d,J=8.8Hz),5.95-6.10(2H,

        ???m),7.36(2H,d,J=5.9Hz),7.47(2H,t,J=7.8Hz),

        ???7.61(1H,t,J=7.8Hz),8.04(2H,d,J=7.8Hz),8.58

        ???(2H,d,J=5.9Hz).

        FAB质谱:861(MH+)。

        本发明实施例71

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?10-脱乙?;?7-脱氧-9-二氢-7氟-9,10-O-(2-吗啉代亚乙基)浆果赤霉素III

        熔点:139-142.5℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.17(3H,s),1.40(9H,s),1.58(3H,s),1.63(6H,s),

        ???1.82(1H,s),2.08-2.35(2H,m),2.28(3H,s),2.37

        ???(1H,dd,J=9.8,15.1Hz),2.40-2.55(1H,m),2.55-

        ???2.67(4H,m),2.85(1H,dd,J=4.4,13.7Hz),2.89(1H,

        ???dd,J=4.4,13.7Hz),3.48(1H,d,J=5.2Hz),3.74

        ???(4H,t,J=4.6Hz),4.10-4.28(1H,br),4.18(1H,d,

        ????J=8.3Hz),4.25(1H,d,J=8.3Hz),4.38(1H,d,J=

        ????8.3Hz),4.61(1H,br?s),4.75(1H,br?d,J=46.4Hz),

        ????4.91(1H,t,J=4.4Hz),4.95(1H,br?d,J=5.9Hz),

        ????5.31(1H,br?d,J=9.1Hz),5.37(1H,d,J=8.3Hz),

        ????5.66(1H,br?d,J=9.1Hz),5.90(1H,d,J=5.2Hz),

        ????6.07(1H,br?t,J=8.3Hz),7.28(1H,t,J=7.3Hz),

        ????7.35(2H,t,J=7.3Hz),7.41(2H,d,J=7.3Hz),7.48

        ????(2H,t,J=7.8Hz),7.61(1H,t,J=7.8Hz),8.09(2H,

        ????d,J=7.8Hz)

        FAB质谱:923(MH+)。

        本发明实施例72

        7α,9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-(4-吡啶基)丙?;?10-脱乙?;?7-脱氧-9-二氢-7氟-9,10-O-异亚丙基浆果赤霉素III

        熔点:154-158℃(由二噁烷冷冻干燥)??1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ?????1.19(3H,s),1.41(9H,s),1.42(3H,s),1.56(3H,s),

        ?????1.61(3H,s),1.62(3H,s),1.63(3H,s),1.87(1H,s),

        ?????2.32(3H,s),2.08-2.47(4H,m),3.46(1H,d,J=

        ?????5.4Hz),4.28-4.40(1H,br),4.31(1H,d,J=8.5Hz),

        ?????4.36(1H,d,J=8.5Hz),4.59(1H,d,J=8.6Hz),4.63

        ?????(1H,br?s),4.87(1H,ddd,J=3.9,7.8,45.9Hz),4.93

        ?????-4.97(1H,m),5.31(1H,br?d,J=9.6Hz),5.52(1H,

        ?????d,J=8.6Hz),5.69(1H,br?d,J=9.6Hz),5.92(1H,d,

        ?????J=5.4Hz),6.12(1H,br?t,J=8.3Hz),7.35(2H,d,

        ?????J=6.2Hz),7.48(2H,t,J=7.6Hz),7.62(1H,t,J=

        ?????7.6Hz),8.10(2H,d,J=7.6Hz),8.60(2H,d,J=

        ?????6.2Hz)

        FAB质谱:853(MH+)。

        本发明实施例73

        7α,9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?10-脱乙?;?7-脱氧-9-二氢-7氟-9,10-O-(2-吗啉代亚乙基)浆果赤霉素III

        ?熔点:134-138.5℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.19(3H,s),1.41(9H,s),1.57(3H,s),1.63(3H,s),

        ???1.72(3H,s),1.81(1H,s),2.10-2.50(4H,m),2.33

        ???(3H,s),2.50-2.75(4H,m),2.82-2.93(2H,m),3.49

        ???(1H,d,J=5.2Hz),3.75(4H,t,J=4.6Hz),4.00(1H,

        ???br?s),4.21(1H,br?d,J=8.8Hz),4.26(1H,d,J=

        ???8.3Hz),4.49(1H,d,J=8.3Hz),4.71(1H,br?s),4.76

        ???(1H,br?d,J=46.5Hz),4.91(1H,t,J=4.2Hz),4.96

        ???(1H,br?d,J=6.4Hz),5.33-5.42(3H,m),5.91(1H,

        ???d,J=5.2Hz),6.10(1H,br?t,J=8.3Hz),6.32(1H,d,

        ???J=2.9Hz),6.34-6.38(1H,m),7.38(1H,br?s),7.49

        ???(2H,t,J=7.3Hz),7.61(1H,t,J=7.3Hz),8.10(2H,

        ???d,J=7.3Hz)

        FAB质谱:913(MH+)。

        本发明实施例74

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?10-脱乙?;?7-脱氧-9-二氢-9,10-O-(2-吗啉代亚乙基)浆果赤霉素III

        熔点:146-149℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)?

        ???1.24(3H,s),1.40(9H,s),1.46(3H,s),1.59(3H,s),

        ???1.60-2.10(5H,m),2.27(3H,s),2.30-2.45(1H,m),

        ???2.58-2.94(6H,m),2.90(1H,d,J=4.4Hz),3.74(4H,

        ???t,J=4.8Hz),4.09(1H,d,J=7.4Hz),4.23(1H,d,

        ???J=8.8Hz),4.31(1H,d,J=8.8Hz),4.50(1H,br),

        ???4.62(1H,s),4.91(1H,s),5.04(1H,t,J=3.9Hz),

        ???5.22(1H,d,J=7.4Hz),5.31(1H,d,J=9.3Hz),5.70

        ???(1H,d,J=9.3Hz),6.05(1H,d,J=4.4Hz),6.05-

        ???6.18(1H,m),7.20-7.48(7H,m),7.60(1H,t,J=

        ???7.3Hz),8.11(2H,d,J=7.3Hz).

        FAB质谱:905(MH+)。

        本发明实施例75

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-(4-吡啶基)丙?;?10-脱乙?;?7-脱氧-9,10-O-亚乙基-9-二氢浆果赤霉素III

        熔点:120-122℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.10-2.10(5H,m),1.23(3H,s),1.25(3H,s),1.42

        ???(9H,s),1.49(3H,d,J=5.3Hz),1.57(3H,s),1.61

        ???(3H,s),2.20-2.40(1H,m),2.26(3H,s),2.90(1H,

        ???d,J=4.9Hz),4.08(1H,d,J=7.3Hz),4.25(1H,d,

        ???J=8.8Hz),4.32(1H,d,J=8.8Hz),4.62(1H,s),4.80

        ???-5.00(2H,m),5.06(1H,q,J=5.3Hz),5.22(1H,d,

        ???J=7.3Hz),5.32(1H,d?like,J=9.3Hz),5.79(1H,d

        ???like,J=9.3Hz),6.03(1H,d,J=4.9Hz),6.05-6.20

        ???(1H,m),7.38(2H,d,J=4.8Hz),7.47(2H,t,J=

        ???7.8Hz),7.60(1H,t,J=7.8Hz),8.11(2H,d,=7.8Hz),

        ???8.61(2H,d,J=4.8Hz).

        FAB质谱:821(MH+)。

        本发明实施例76

        9β-13-O-〔3-(叔丁氧基羰基氨基)-2-乙基-2-羟基-3-(4-吡啶基)丙?;?4-O-环丙烷羰基-4,10-二脱乙?;?9-二氢-9,10-O-异亚丙基浆果赤霉素III

        熔点:125-164℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.95(3H,t,J=6.8Hz),1.11-1.48(6H,m),1.25(6H,

        ???s),1.29?3H,s),1.66(3H,s),1.90-2.37(5H,m),

        ???2.89(1H,d,J=4.4Hz),3.71(1H,d,J=7.3Hz),4.06

        ???(1H,m),4.31(2H,s),4.67(1H,d,J=8.3Hz),5.01

        ???(1H,d,J=9.8Hz),5.05(1H,s),5.45(1H,d,J=

        ???6.8Hz),5.91(1H,d,J=9.8Hz),6.07(1H,d,J=

        ???4.4Hz),6.21(1H,t,J=8.0Hz),7.36(2H,d,=

        ???5.9Hz),7.49(2H,t,J=7.3Hz),7.62(1H,t,J=

        ???7.3Hz),8.04(2H,d,J=8.3Hz),8.56(2H,d,J=

        ???5.4Hz).

        FAB质谱:905(MH+)。

        本发明实施例77

        9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?10-脱乙?;?7-脱氧-9-二氢-9,10-O-(2-亚丙烯基)浆果赤霉素III

        熔点:133-136℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.26(3H,s),1.42(9H,s),1.49(3H,s),1.63(3H,s),

        ???1.75(3H,s),1.80-2.15(5H,m),2.30-2.44(1H,m),

        ???2.33(3H,s),2.93(1H,d,J=4.9Hz),4.17(1H,d,J=

        ???6.8Hz),4.23(1H,d,J=8.8Hz),4.33(1H,d,J=

        ???8.8Hz),4.72(1H,s),4.92(1H,s),5.24(1H,d,J=

        ??6.3Hz),5.30(1H,d,J=6.8Hz),5.38(1H,d,J=

        ??10.2Hz),5.42-5.54(2H,m),5.58(1H,d,J=17.5Hz),

        ??5.96-6.08(2H,m),6.11(1H,t,J=7.9Hz),6.31(1H,

        ??d,J=3.4Hz),6.34(1H,dd,J=3.4Hz,J=1.9Hz),

        ??7.39(1H,s?like),7.47(2H,t,J=7.8Hz),7.60(1H,

        ??t,J=7.8Hz),8.12(2H,d,J=7.8Hz).

        FAB质谱:822(MH+)。

        本发明实施例78

        9β-13-O-〔3-(叔丁氧基羰基氨基)-2-乙基-2-羟基-3-(4-吡啶基)丙?;?10-脱乙?;?9-二氢-9,10-O-异亚丙基浆果赤霉素III

        熔点:16l-163℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.95(3H,t,J=7.3Hz),1.26(3H,s),1.30(3H,s),

        ???1.36(9H,s),1.39(3H,s),1.57(3H,s),1.62(3H,s),

        ???1.67(3H,s),1.82-2.35(4H,m),2.49(3H,s),2.89

        ???(1Hd,J=4.4Hz),3.75(1H,d,J=7.3Hz),4.06(1H,

        ???br),4.38(2H,s),4.67(1H,d,J=7.8Hz),5.01(1H,

        ???d,J=9.8Hz),5.10(1H,s),5.45(1H,d,J=6.8Hz),

        ???5.82(1H,brd,J=9.3Hz),6.04(1H,d,J=4.4Hz),

        ???6.24(1H,t,J=8.0Hz),7.36(2H,d,J=5.4Hz),7.48

        ???(2H,t,J=7.8Hz),7.60(1H,t,J=7.3Hz),8.24(2H,

        ???d,J=7.3Hz),8.56(2H,d,J=5.4Hz).

        FAB质谱:879(MH+)。

        本发明实施例79

        9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?10-脱乙?;?7-脱氧-9-二氢-9,10-O-(2-吗啉代亚乙基)浆果赤霉素III

        熔点:140-143℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.25(3H,s),1.41(9H,s),1.47(3H,s),1.60(3H,s),

        ???1.60-2.15(5H,m),1.73(3H,s),2.20-2.42(1H,m),

        ???2.32(3H,s),2.52-2.84(6H,m),2.92(1H,d,J=

        ???4.9Hz),3.74(4H,t,J=4.4Hz),4.11(1H,d,J=

        ???6.9Hz),4.23(1H,d,J=8.3Hz),4.32(1H,d,J=

        ???8.3Hz),4.72(1H,s),4.91(1H,s),5.0481?H,t,J=

        ???3.9Hz),5.24(1H,d,J=6.9Hz),5.45(1H,d,J=

        ???9.3Hz),5.99(1H,d,J=4.9Hz),6.03-6.18(1H,m),

        ???6.31(1H,s?like),6.34(1H,s?like),7.38(1H,s

        ???like),7.47(2H,t,J=7.8Hz),7.60(1H,t,J=

        ???7.8Hz),8.12(2H,d,J=7.8Hz).

        FAB质谱:895(MH+)。

        本发明实施例80

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-(2-吡啶基)丙?;?10-脱乙?;?7-脱氧-9-二-氢-9,10-O-异亚丙基浆果赤霉素III

        熔点:145-148℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)????

        ???1.26(3H,s),1.43(3H,s),1.44(9H,s),1.52(3H,s),

        ???1.56(3H,s),1.61(3H,s),1.71(3H,s),1.80-2.20

        ???(4H,m),2.22-2.31(2H,m),2.35(3H,s),2.94(1H,

        ???d,J=4.9Hz),4.17(1H,d,J=7.3Hz),4.23(1H,d,

        ???J=8.3Hz),4.32(1H,d,J=8.3Hz),4.88(1H,d,J=

        ???2.5Hz),4.92(1H,s),5.34(1H,d,J=9.3Hz),5.56

        ???(1H,d,J=7.3Hz),5.94(1H,d,J=9.3Hz),5.96(1H,

        ???d,J=4.9Hz),6.09(1H,t,J=8.3Hz),7.22(1H,dd,

        ???J=7.3Hz,J=4.9Hz),7.38-7.50(3H,m),7.59(1H,t,

        ???J=7.8Hz),7.72(1H,t,J=7.3Hz),8.12(2H,d,J=

        ???7.8Hz),8.54(1H,d,J=4.4Hz).

        FAB质谱:835(MH+)。

        本发明实施例81????

        7α,9β-4-O-丁?;?13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?7-脱氧-4,10-二脱乙?;?9-二氢-7氟-9,10-O-(2-吗啉代亚乙基)浆果赤霉素III

        熔点:124.5-129.5℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.02(3H,t,J=7.3Hz),1.19(3H,s),1.40(9H,s),

        ???1.57(3H,s),1.63(3H,s),1.72(3H,s),1.81(1H,s),

        ???1.75-1.90(2H,m),2.15-2.55(6H,m),2.55-2.67

        ???(4H,m),2.82-2.93(2H,m),3.49(1H,d,J=5.4Hz),

        ???3.74(4H,t,J=5.1Hz),3.92(1H,br?s),4.22(1H,d,

        ???J=8.3Hz),4.27(1H,d,J=8.3Hz),4.39(1H,d,J=

        ???8.3Hz),4.66-4.73(1H,br),4.68-4.85(1H,m),4.87

        ???-4.95(2H,m),5.30-5.41(3H,m),5.91(1H,d,J=

        ???5.4Hz),6.08(1H,br?t,J=8.1Hz),6.33(1H,d,J=

        ???3.4Hz),6.36(1H,dd,J=3.4,1.5Hz),7.39(1H,d,J=

        ???1.5Hz),7.48(2H,t,J=7.8Hz),7.62(1H,t,J=

        ???7.8Hz),8.11(2H,d,J=7.8Hz)

        本发明实施例82

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-2-甲基-3-(2-吡啶基)丙?;?10-脱乙?;?7-脱氧-9-二氢-9,10-O-异亚丙基浆果赤霉素III

        熔点:147-150℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.29(3H,s),1.40(3H,s),1.42(9H,s),1.52(3H,s),

        ???1.54(3H,s),1.55(6H,s),1.61(3H,s),1.80-2.23

        ???(6H,m),2.51(3H,s),2.94(1H,d,J=4.9Hz),4.18

        ???(1H,d,J=7.3Hz),4.22(1H,d,J=7.3Hz),4.34(1H,

        ???d,J=8.3Hz),4.94(1H,s),5.10(1H,d,J=10.2Hz),

        ???5.49(1H,d,J=7.3Hz),6.03(1H,d,J=10.2Hz),6.15

        ???(1H,t,J=8.8Hz),7.18-7.33(1H,m),7.37-7.55

        ???(3H,m),7.60(1H,t,J=7.4Hz),7.67-7.80(1H,m),

        ???8.15(2H,d,J=7.4Hz),8.49(1H,d,J=4.4Hz).

        FAB质谱:849(MH+)。

        本发明实施例83

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-2-甲基-3-(2-吡啶基)丙?;?4,10-二脱乙?;?9-二氢-9,10-O-异亚丙基-4-O-丙?;嗝顾豂II

        熔点:148-150℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.28(3H,s),1.32(3H,t,J=7.5Hz),1.40(3H,s),

        ???1.44(9H,s),1.58(3H,s),1.65(3H,s),1.66(3H,s),

        ???2.18(2H,br),2.27(1H,m),2.68(2H,q,J=7.5Hz),

        ???2.96(1H,d,J=4.9Hz),3.88(1H,d,J=7.3Hz),4.06

        ???(1H,m),4.32(1H,d,J=8.3Hz),4.41(1H,d,J=

        ???8.3Hz),4.68(1H,d,J=7.8Hz),4.85(1H,br),5.05

        ???(1H,t-br),5.32(1H,m),5.52(1H,d,J=7.3Hz),

        ???5.87(1H,d,J=9.9Hz),6.03(1H,d,J=4.9Hz),6.09

        ???(1H,t,J=8.8Hz),7.24(1H,m),7.42(1H,d,J=

        ???7.8Hz),7.47(2H,t,J=7.5Hz),7.60(1H,t,J=

        ???7.5Hz),7.73(1H,td,J=7.8Hz,2Hz),8.13(2H,m),

        ???8.52(1H,d,J=4.4Hz).

        FAB质谱:866(MH+)。

        本发明实施例84

        9β-13-O-〔3-(叔丁氧基羰基氨基)-2-羟基-2-甲基-3-(2-吡啶基)丙?;?10-脱乙?;?9-二氢-9,10-O-异亚丙基浆果赤霉素III

        熔点:145-151℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.29(3H,s),1.38(3H,s),1.44(9H,s),1.50(3H,s),

        ???1.55(3H,s),1.56(3H,s),1.64(3H,s),1.66(3H,s),

        ???2.07-2.30(4H,m),2.55(3H,s),2.94(1H,d,J=

        ???5.4Hz),3.86(1H,d,7.3Hz),4.05(1H,m),4.36(2H,

        ???ABq,J=8.3Hz),4.69(1H?d,J=7.8Hz),5.10(1H,d,

        ???J=10.3Hz),5.11(1H,s?like),5.45(1H,d,J=

        ???7.8Hz),5.99-6.03(2H,m),6.16(1H,t,J=9.3Hz),

        ???7.24(1H,m),7.43-7.48(3H,m),7.60(1H,t,J=

        ???7.3Hz),7.73(1H,t,J=6.8Hz),8.14(2H,d,J=

        ???7.8Hz),8.47(1H,d,J=4.4Hz).

        FAB质谱:865(MH+)。

        本发明实施例85

        9β-13-O-〔3-(叔丁氧基羰基氨基)-2-羟基-2-甲基-3-(2-吡啶基)丙?;?4,10-二脱乙?;?9-二氢-9,10-O-异亚丙基-4-O-丙?;嗝顾豂II

        熔点:147-150℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.30(s),1.38(s),1.40(3H,t,J=7.3Hz),1.44(9H,

        ???s),1.50(s),1.55(s),1.57(s),1.64(s),1.65(s),

        ???2.12(1H,dd,J=14.7Hz,8.8Hz),2.20(2H,t,J=

        ???3.4Hz),2.29(1H,dd,J=14.7Hz,8.8Hz),2.88(2H,q,

        ???J=7.5Hz),2.94(1H,d,J=5.4Hz),3.88(1H,d,J=

        ???7.3Hz),4.05(1H,m),4.32(1H,d,J=8.3Hz),4.44

        ???(1H,d,J=8.3Hz),4.67(1H,d,J=7.8Hz),5.07(1H,

        ?????m),5.45(1H,d,J=7.3Hz),6.01(2H,m),6.14(1H,t,

        ?????J=9Hz),7.24(1H,m),7.44(1H,d,J=8.3Hz),7.48

        ?????(2H,t,J=7.8Hz),7.60(1H,t,J=7.3Hz),7.73(1H,

        ?????td,J=7.5Hz,1.5Hz),8.14(2H,m),8.47(1H,d,J=

        ?????4.4Hz).

        FAB质谱:879(M+)。

        本发明实施例86

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-(2-吡啶基)丙?;?10-脱乙?;?9-二氢-9,10-O-异亚丙基浆果赤霉素III

        熔点:150-153℃(由二噁烷冷冻干燥)??1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ?????1.27(3H,s),1.40(3H,s),1.44(9H,s),1.58(3H,s),

        ?????1.64(3H,s),1.66(3H,s),1.69(3H,s),2.05-2.32

        ?????(4H,m),2.40(3H,s),2.95(1H,d,J=4.9Hz),3.86

        ?????(1H,d,J=7.8Hz),4.06(1H,m),4.35(2H,ABq,J=

        ?????8.3Hz),4.70(d,J=8.3Hz),4.85(1H,d,J=2.4Hz),

        ?????5.11(1H,s),5.35(1H.d,J=9.3Hz),5.53(1H,d,J=

        ?????7.3Hz),5.90(1H,d,J=9.8Hz),6.03(1H,d,J=

        ?????5.4Hz),6.10(1H,t,J=8.3Hz),7.24(1H,m),7.41

        ?????(1H,d,J=7.8Hz),7.47(2H,t,J=7.8Hz),7.59(1H,

        ?????t,J=7.3Hz),7.73(1H,t,J=5.9Hz),8.11(2H,d,

        ?????J=8.8Hz),8.52(1H,d,J=4.9Hz).

        FAB质谱:852(MH2+)。

        本发明实施例87

        9β-13-O-〔3-(叔丁氧基羰基氨基)-2-羟基-2-甲基-3-(2-吡啶基)丙?;?10-脱乙?;?9-二氢-9,10-O-(2-亚丙烯基)浆果赤霉素III

        熔点:140-145℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.30(3H,s),1.44(9H,s),1.52(3H,s),1.54(3H,s),

        ???1.62(3H,s),1.68(3H,s),2.13-2.30(4H,m),2.55

        ???(3H,s),2.95(1H,d,J=4.9Hz),3.89(1H,d,J=

        ???6.8Hz),4.08(1H,m),4.35(2H,ABq,J=8.3Hz),4.61

        ???(1H,d,J=8.3Hz),5.12(3H,m),5.19(1H,d,J=

        ???6.4Hz),5.45(1H,d,J=10.7Hz),5.56(1H,d,J=

        ???17.6Hz),6.01(2H,m),6.17(2H,m),7.24(1H,m),7.43

        ???-7.51(3H,m),7.61(1H,t,J=7.3Hz),7.73(1H,t,

        ???J=6.4Hz),8.13(2H,d,J=7.3Hz),8.48(1H,d,J=

        ???4.4Hz).

        FAB质谱:864(MH2+)。

        本发明实施例88

        9β-13-O-〔3-(叔丁氧基羰基氨基)-2-羟基-2-甲基-3-(2-吡啶基)丙?;?10-脱乙?;?9-二氢-9,10-O-(2-吗啉代亚乙基)浆果赤霉素III

        熔点:135-139℃(由二噁烷冷冻干燥)1H-NMH(400?MHz,CDCl3/TMS)δ(ppm)????

        ???1.30(3H,s),1.43(9H,s),1.51(3H,s),1.54(3H,s),

        ???1.61(3H,s),1.64(3H,s),2.09-2.34(4H,m),2.55

        ???(3H,s),2.62(4H,m),2.77(2H,ABdq,J=26.9Hz,

        ???3.4Hz),2.95(1H,d,J=4.9Hz),3.73(4H,t?like,

        ???4.9Hz),3.81(1H,d,J=7.3Hz),4.07(1H,m),4.35

        ???(2H,ABq,J=8.3Hz),4.71(1H,d,J=8.3Hz),4.99

        ???(1H,t,J=4.4Hz),5.10(1H,d,J=10.3Hz),5.12(1H,

        ???d,J=7.3Hz),6.01(1H,d,J=5.4Hz),6.02(1H,d,

        ???J=4.9Hz),6.16(1H,t,J=7.8Hz),7.23(1H,m),7.43

        ???(1H,d,J=7.8Hz),7.49(2H,t,J=7.8Hz),7.61(1H,

        ???t,J=7.8Hz),7.73(1H,t,J=7.8Hz),8.13(2H,d,

        ???J=7.3Hz),8.47(1H,d,J=4.9Hz).

        FAB质谱:936(MH+)。

        本发明实施例89

        9β-13-O-〔(2R,3S)-3-(苄基氨基)-2-羟基-3-苯基丙?;?4-O-环丙烷羰基-4,10-二脱乙?;?7-脱氧-9-二氢-9,10-O-(2-亚丙烯基)浆果赤霉素III

        熔点:150-153℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.05-1.13(2H,m),1.21(3H,s),1.38-1.50(2H,m),

        ???1.43(3H,s),1.46(3H,s),1.55-1.75(2H,m),1.60

        ???(3H,s),1.78-2.11(5H,m),2.38(1H,dd,J=15.1Hz,

        ???J=9.7Hz),2.85(1H,d,J=4.9Hz),4.09(1H,d,J=

        ???6.9Hz),4.18(1H,d,J=8.8Hz),4.27(1H,d,J=

        ???8.8Hz),4.73(1H,s?like),4.88(1H,s?like),4.93(1H,

        ???s?like),5.18-5.27(2H,m),5.44(1H,d,J=10.3Hz),

        ???5.55(1H,d,J=17.1Hz),5.85(1H,dd,J=9.3Hz,J=

        ???2.5Hz),5.94-6.09(3H,m),7.24-7.57(11H,m),7.60

        ???(1H,t,J=7.3Hz),7.84(2H,d?like,J=8.3Hz),8.04

        ???(2H,d,J=7.3Hz).

        FAB质谱:862(MH+)。

        本发明实施例90

        9β-13-O-〔3-(叔丁氧基羰基氨基)-2-羟基-2-甲基-3-(4-吡啶基)丙?;?4,10-二脱乙?;?9-二氢-9,10-O-异亚丙基-4-O-丙?;嗝顾豂II

        熔点:152-155℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)????

        ???1.30(s),1.38(s),1.40(s),1.41(s),1.44(s),1.58

        ???(s),1.68(s),2.06(1H,m),2.10(1H,m),2.22(1H,

        ???m),2.26(1H,m),2.63(1H,m),2.75(1H,m),2.91(1H,

        ???d,J=4.4Hz),3.78(1H,d,J=7.8Hz),4.08(1H,br),

        ???4.39(2H,ABq,J=8.8Hz),4.70(1H,d,J=7.8Hz),

        ???4.99(1H,d,J=9.8Hz),5.48(1H,d,J=7.3Hz),5.78

        ???(1H,d,J=9.8Hz),6.06(1H,d,J=4.3Hz),6.21(1H,

        ???t-br),7.35(2H,d,J=5Hz),7.48(2H,t,J=

        ???7.8Hz),7.61(1H,t,J=7.3Hz),8.14(2H,m),8.59

        ???(2H,d,J=5Hz).

        FAB质谱:879(M+)。

        本发明实施例91

        9β-13-O-〔(2R,3S)-3-(苄基氨基)-2-羟基-3-苯基丙?;?4-O-环丙烷羰基-4,10-二脱乙?;?7-脱氧-9-二氢-9,10-O-(2-吗啉代亚乙基)浆果赤霉素III

        熔点:150-153℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.04-1.13(2H,m),1.21(3H,s),1.36-1.47(2H,m),

        ???1.42(3H,s),1.44(3H,s),1.53-2.08(7H,m),1.57

        ???(3H,s),2.37(1H,dd,J=15.1Hz,J=9.8Hz),2.53-

        ???2.73(5H,m),2.77(1H,dd,J=13.6Hz,J=3.9Hz),

        ???2.85(1H,d,J=4.4Hz),3.73(4H,t,J=4.4Hz),4.17

        ???(1H,d,J=6.8Hz),4.26(1H,d,J=8.8Hz),4.30(1H,

        ???d,J=8.8Hz),4.73(1H,d,J=2.4Hz),4.87(1H,br

        ???s),5.00(1H,t,J=4.4Hz),5.14(1H,d,J=6.8Hz),

        ???5.85(1H,dd,J=9.3Hz,J=2.5Hz),5.97-6.06(2H,

        ???m),7.23-7.56(10H,m),7.60(1H,t,J=7.3Hz),7.84

        ???(1H,d,J=7.3Hz),8.04(2H,d,J=7.3Hz).

        FAB质谱:935(MH+)。

        本发明实施例92

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?4-O-乙氧基羰基-4,10-二脱乙?;?9-二氢-9,10-O-(2-亚丙烯基)浆果赤霉素III

        熔点:117-120℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm),

        ???1.24(3H,s),1.34(3H,t,J=7.4Hz),1.40(9H,s),

        ???1.62(3H,s),1.65(3H,br?s),1.67(3H,s),1.88(1H,

        ???s),1.99-2.29(3H,m);2.47(1H,dd,J=15.1Hz,J=

        ???9.7Hz),2.86(1H,d,J=4.3Hz),3.87(1H,d,J=

        ???6.8Hz),3.97(1H,br),4.08(1H,m),4.30-4.66(6H,

        ???m),5.17-5.36(3H,m),5.45(1H,d,J=10.8Hz),5.57

        ???(1H,d,J=17.1Hz),5.66(1H,d,J=9.7Hz),5.92(1H,

        ???br?t,J=7.3Hz),6.03(1H,ddd,J=17.1Hz,J=

        ???10.8Hz,J=6.3Hz),6.11(1H,d,J=4.3Hz),7.24-

        ???7.49(7H,m),7.58(1H,t,J=7.3Hz),8.03(2H,d,J=

        ???7.3Hz).

        FAB质谱:878(MH+)。

        本发明实施例93

        9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?4-O-乙氧基羰基-4,10-二脱乙?;?9-二氢-9,10-O-(2-亚丙烯基)浆果赤霉素III

        熔点:121-123℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.26(3H,s),1.37(3H,t,J=6.9Hz),1.38(9H,s),

        ???1.63(3H,s),1.68(3H,s),1.75(3H,s),1.88(1H,s),

        ???2.02-2.12(1H,m),2.18-2.37(2H,m),2.45(1H,dd,

        ???J=15.2Hz,J=9.8Hz),2.88(1H,d,J=4.9Hz),3.80-

        ???3.94(2H,m),4.08(1H,br),4.29-4.61(5H,m),4.70

        ???(1H,s?like),5.18-5.29(2H,m),5.29(1H,d,J=

        ???7.0Hz),5.30-5.45(2H,m),5.46(1H,d,J=10.7Hz),

        ???5.57(1H,d,J=17.0Hz),5.97-6.15(2H,m),6.10

        ???(1H,d,J=4.9Hz),7.38(1H,s?like),7.44(2H,t,J=

        ???7.8Hz),7.58(1H,t,J=7.8Hz),8.05(2H,d,J=

        ???7.8Hz).

        FAB质谱:868(MH+)。

        本发明实施例94

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?4-O-乙氧基羰基-4,10-二脱乙?;?9-二氢-9,10-O-(2-吗啉代亚乙基)浆果赤霉素III

        熔点:128-131℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.24(3H,s),1.33(3H,t,J=7.3Hz),1.40(9H,s),

        ???1.60(3H,s),1.64(6H,s),1.86(1H,s),2.00-2.09

        ???(1H,m),2.14-2.30(2H,m),2.46(1H,dd,J=15.1Hz,

        ???J=9.7Hz),2.56-2.71(4H,m),2.75(1H,dd,J=

        ???13.6Hz,J=5.3Hz),2.80-2.91(2H,m),3.73(4H,t,

        ???J=5.3Hz),3.78(1H,d,J=7.3Hz),4.06(1H,br),

        ???4.29-4.48(3H,m),4.50-4.68(3H,m),5.03(1H,t

        ???like,J=5.3Hz),5.19-5.35(3H,m),5.65(1H,d,J=

        ???9.8Hz),5.92(1H,br?t,J=6.8Hz),6.09(1H,d,J=

        ???4.4Hz),7.25-7.50(7H,m),7.59(1H,t,J=7.8Hz),

        ???8.03(2H,d,J=7.8Hz).

        FAB质谱:951(MH+)。

        本发明实施例95

        9β-13-O-〔3-(叔丁氧基羰基氨基)-2-羟基-2-甲基-3-(4-吡啶基)丙?;?10-脱乙?;?7-脱氧-9-二氢-9,10-O-异亚丙基浆果赤霉素III

        熔点:182-184℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.27(3H,s),1.37(9H,s),1.42(6H,s),1.47(3H,br

        ???s),1.50(3H,s),1.56(3H,s),1.62(3H,s),1.75-

        ???2.11(6H,m),2.22(1H,dd,J=14.2Hz,J=10.2Hz),

        ???2.30-2.50(1H,m),2.42(3H,s),2.91(1H,d,J=

        ???4.4Hz),4.12(1H,d,J=7.3Hz),4.28(1H,d,J=

        ???8.3Hz),4.32(1H,d,J=8.3Hz),4.58(1H,br),4.92

        ???(1H,s),5.00(1H,d,J=10.2Hz),5.51(1H,d,J=

        ???7.3Hz),5.92(1H,d,J=10.2Hz),5.98(1H,d,J=

        ???4.4Hz),6.17-6.29(1H,m),7.36(2H,d,J=5.4Hz),

        ???7.47(2H,t,J=7.9Hz),7.60(1H,t,J=7.9Hz),8.13

        ???(2H,d,J=7.9Hz),8.58(2H,d,J=5.4Hz).

        FAB质谱:849(MH+)。

        本发明实施例96

        9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?4-O-乙氧基羰基-4,10-二脱乙?;?9-二氢-9,10-O-(2-吗啉代亚乙基)浆果赤霉素III?

        熔点:130-132℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.26(3H,s),1.36(3H,t,J=6.8Hz),1.41(9H,s),

        ???1.61(3H,s),1.65(3H,s),1.73(3H,s),1.85(1H,s),

        ???2.00-2.10(1H,m),2.19-2.39(2H,m),2.42(1H,dd,

        ???J=15.1Hz,J=9.8Hz),2.54-2.93(7H,m),3.73(4H,

        ???t,J=4.4Hz),3.80(1H,d,J=7.3Hz),4.06(1H,br),

        ???4.25-4.50(3H,m),4.53(1H,d,J=8.8Hz),4.61(1H,

        ???d,J=7.8Hz),4.70(1H,s),5.03(1H,t,J=4.4Hz),

        ???5.17-5.45(4H,m),5.99(1H,t,J=7.8Hz),6.08(1H,

        ???d,J=4.4Hz),6.28-6.42(2H,m),7.38(1H,s?like),

        ???7.45(2H,t,J=7.8Hz),7.59(1H,t,J=7.8Hz),8.05

        ???(2H,d,J=7.8Hz).

        FAB质谱:941(MH+)。

        本发明实施例97

        9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-2-羟基-3-(2-噻吩基)丙?;?10-脱乙?;?7-脱氧-9-二氢-9,10-O-(2-亚丙烯基)浆果赤霉素III

        熔点:135-137℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDC13/TMS)δ(ppm)

        ???1.24(3H,s),1.41(9H,s),1.48(3H,s),1.63(3H,s),

        ???1.66(3H,s),1.80-2.22(5H,m),2.31(3H,s),2.37

        ???(1H,dd,J=15.1Hz,J=10.2Hz),2.92(1H,d,J=

        ???5.3Hz),4.16(1H,d,J=6.9Hz),4.24(1H,d,J=

        ???8.8Hz),4.33(1H,d,J=8.8Hz),4.57(1H,s),4.64

        ???(1H,s),4.93(1H,s),5.23(1H,d,J=6.4Hz),5.29

        ???(1H,d,J=6.9Hz),5.46(1H,d,J=10.8Hz),5.505.74

        ???(3H,m),5.96-6.18(3H,m),6.98(1H,dd,J=5.4Hz,

        ???J=4.0Hz),7.10(1H,d,J=4.0Hz),7.22-7.27(1H,

        ???m),7.47(2H,t,J=7.8Hz),7.60(1H,t,J=7.8Hz),

        ???8.12(2H,d,J=7.8Hz).

        FAB质谱:838(MH+)。

        本发明实施例98

        9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-2-羟基-3-(2-噻吩基)丙?;?10-脱乙?;?7-脱氧-9-二氢-9,10-O-(2-吗啉代亚乙基)浆果赤霉素III

        熔点:135-138℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.24(3H,s),1.41(9H,s),1.47(3H,s),1.59(3H,s),

        ???1.60-2.15(5H,m),1.65(3H,s),2.31(3H,s),2.36

        ???(1H,dd,J=15.2Hz,J=9.8Hz),2.57-2.86(6H,m),

        ???2.91(1H,d,J=4.9Hz),3.74(4H,t,J=4.8Hz),4.10

        ???(1H,d,J=6.8Hz),4.23(1H,d,J=8.3Hz),4.32(1H,

        ???d,J=8.3Hz),4.64(1H,s),4.92(1H,s),5.04(1H,t,

        ???J=3.9Hz),5.22(1H,d,J=6.8Hz),5.54(1H,d,J=

        ???9.8Hz),5.60(1H,d,J=9.8Hz),5.99(1H,d,J=

        ???4.9Hz),6.08(1H,t,J=7.8Hz),6.97(1H,dd,J=

        ???5.3Hz,J=3.4Hz),7.10(1H,d,J=3.4Hz),7.20-7.20

        ???(1H,m),7.47(2H,t,J=7.8Hz),7.61(1H,t,J=

        ???7.8Hz),8.12(2H,d,J=7.8Hz).

        FAB质谱:911(MH+)。

        本发明实施例99

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-(2-吡啶基)丙?;?4,10-二脱乙?;?9-二氢-4-O-乙氧基羰基-9,10-O-异亚丙基浆果赤霉素III

        熔点:131-135℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.25(3H,s),1.37(3H,t,J=7.3Hz),1.41(3H,s),

        ???1.45(9H,s),1.59(3H,s),1.65(6H,s),1.74(3H,s),

        ???1.87-2.39(1H,d,J=4.4Hz),2.86(1H,d,J=

        ???4.4Hz),3.63(1H,d,J=7.3Hz),4.04(1H,m),4.34

        ???(2H,m),4.48(1H,q,7.3Hz),4.53(1H,d,J=8.8Hz),

        ???4.67(1H,d,J=7.8Hz),4.80(1H,d,J=2.8Hz),5.23

        ???(1H,d,J=7.8Hz),5.57(1H,d,J=7.3Hz),5.59(2H,

        ???m),6.07(1H,d,J=4.9Hz),7.24(1H,dd,J=7.3Hz,

        ???4.9Hz),7.45(2H,t,J=7.8Hz),7.58(1H,t,J=

        ???7.3Hz),7.73(1H,dt,7.8Hz,2.0Hz),8.05(2H,d,J=

        ???7.2Hz),8.50(1H,d,J=3.9Hz).

        FAB质谱:881(MH+)。

        本发明实施例100

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-(4-吡啶基)丙?;?4,10-二脱乙?;?9-二氢-4-O-乙氧基羰基-9,10-O-异亚丙基浆果赤霉素III

        熔点:132-137℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.23(3H,s),1.37(3H,t,J=7.3Hz),1.41(9H,s),

        ???1.59(3H,s),1.62(3H,s),1.64(3H,s),1.66(6H,s),

        ???2.02-2.48(4H,m),2.87(1H,d,J=4.4Hz),3.79(1H,

        ???d,J=7.3Hz),4.06(1H,m),4.35(1H,d,J=8.8Hz),

        ???4.43(2H,q,J=7.3Hz),4.52(1H,d,J=8.8Hz),4.62

        ???(2H,s),5.21(1H,s),5.30(1H,d,J=8.3Hz),5.66

        ???(1H,d,J=7.3Hz),5.75(1H,d,J=9.8Hz),5.94(1H,

        ???t,J=8.0Hz),6.12(1H,d,J=4.4Hz),7.37(2H,d,

        ???J=4.9Hz),7.44(2H,t,J=7.8Hz),7.60(1H,t,J=

        ???7.8Hz),8.03(2H,d,J=7.3Hz),8.60(2H,d,J=

        ???5.4Hz).

        FAB质谱:881(MH+)。

        本发明实施例101

        9β-13-O-〔3-(叔丁氧基羰基氨基)-2-羟基-2-甲基-3-(4-吡啶基)丙?;?4,10-二脱乙?;?9-二氢-4-O-乙氧基羰基-9,10-O-异亚丙基浆果赤霉素III

        熔点:149-153℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.28(3H,s),1.38(9H,s),1.41(3H,s),1.42(3H,s),

        ???1.45(3H,t,J=7.3Hz),1.53(3H,s),1.59(3H,s),

        ???1.65(3H,s),1.67(3H,s),2.02-2.27(4H,m),2.91

        ???(1H,d,J=3.9Hz),3.78(1H,d,J=7.3Hz),4.06(1H,

        ???m),4.53(1H,d,J=8.8Hz),4.54(3H,m),4.63(1H,

        ???d,7.8Hz),5.09(1H,d,J=10.3Hz),5.21(1H,s),5.53

        ???(1H,d,J=7.3Hz),5.82(1H,d,J=9.8Hz),6.10(1H,

        ???d,J=4.4Hz),6.17(1H,t,J=8.3Hz),7.39(2H,d,

        ???J=4.9Hz),7.44(2H,t,J=7.8Hz),7.59(1H,t,J=

        ???7.3Hz),8.05(2H,d,J=7.3Hz),8.58(2H,d,J=

        ???4.9Hz).

        FAB质谱:895(MH+)。

        本发明实施例102

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?10-脱乙?;?7-脱氧-9-二氢-9,10-O-硫代碳酸酯浆果赤霉素III

        熔点:162-165℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.25(3H,s),1.30(3H,s),1.40(9H,s),1.50-2.15(5H,

        ???m),1.61(3H,s),1.62(3H,s),2.29(3H,s),2.41(1H,

        ???dd,J=15.2Hz,J=9.8Hz),2.87(1H,d,J=4.9Hz),

        ???4.10(1H,br),4.20(1H,d,J=8.8Hz),4.32(1H,d,

        ???J=8.8Hz),4.63(1H,br),4.85(1H,d,J=8.7Hz),

        ???4.90(1H,s),5.28(1H,d,J=9.2Hz),5.58(1H,d,J=

        ???9.2Hz),5.99(1H,d,J=4.9Hz),6.04-6.18(2H,m),

        ???7.20-7.45(5H,m),7.48(2H,t,J=7.8Hz),7.62(1H,

        ???t,J=7.8Hz),8.10(2H,d,J=7.8Hz).

        FAB质谱:836(MH+)。

        本发明实施例103

        7α,9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-(2-吡啶基)丙?;?10-脱乙?;?7-脱氧-9-二氢-7-氟-9,10-O-异亚丙基浆果赤霉素III

        熔点:136-141℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.21(3H,s),1.42(3H,s),1.44(9H,s),1.52(3H,s),

        ???1.59(3H,s),1.65(3H,s),1.70(1H,s),1.74(3H,s),

        ???2.07-2.45(4,m),2.27(1H,d,J=9.3Hz),2.41(3H,

        ???s),3.50(1H,d,J=5.4Hz),4.29(1H,d,J=8.8Hz),

        ???4.36(1H,d,J=8.8Hz),4.62(1H,d,J=9.1Hz),4.84

        ???(1H,br?s),4.83-5.02(1H,m),4.95-5.02(1H,m),

        ???5.36(1H,br?d,J=9.8Hz),5.53(1H,d,J=9.1Hz),

        ???5.86-5.95(2H,m),6.10(1H,br?t,J=8.5Hz),7.23

        ???(1H,dd,J=4.9,7.1Hz),7.41(1H,d,J=7.8Hz),7.48

        ???(2H,t,J=7.3Hz),7.60(1H,t,J=7.3Hz),7.73(1H,

        ???dt,J=1.5,7.8Hz),8.21(2H,d,J=7.63z),8.46(1H,

        ???d,J=4.9Hz)

        FAB质谱:853(MH+)。

        本发明实施例104

        9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?10-脱乙?;?7-脱氧-9-二氢-9,10-O-〔2-(1-甲基哌嗪-4-基)亚乙基〕浆果赤霉素III

        熔点:128-130℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.25(3H,s),1.42(9H,s),1.47(3H,s),1.58-2.10

        ???(6H,m),1.60(3H,s),1.73(3H,s),2.20-2.88(9H,

        ???m),2.32(6H,s),2.91(1H,d,J=4.9Hz),4.11(1H,d,

        ???J=6.9Hz),4.23(1H,d,J=8.3Hz),4.32(1H,d,J=

        ???8.3Hz),4.77(1H,s?like),4.91(1H,s?like),5.03(1H,

        ???t,J=3.9Hz),5.23(1H,d,J=6.9Hz),5.37(1H,d,

        ???J=9.3Hz),5.43(1H,d,J=9.3Hz),5.99(1H,d,J=

        ???4.9Hz),6.10(1H,t,J=8.0Hz),6.31(1H,d,J=

        ???3.4Hz),6.35(1H,dd,J=3.4Hz,J=1.9Hz),7.39(1H,

        ???d,J=1.9Hz),7.47(2H,t,J=7.8Hz),7.60(1H,t,

        ???J=7.8Hz),8.12(2H,d,J=7.8Hz).

        FAB质谱:908(MH+)。

        本发明实施例105

        9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?10-脱乙?;?7-脱氧-9-二氢-9,10-O-(2-二甲基氨基亚乙基)浆果赤霉素III

        熔点:135-136℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.25(3H,s),1.42(9H,s),1.47(3H,s),1.61(3H,s),

        ???1.70-2.10(5H,m),1.74(3H,s),2.20-2.35(1H,m),

        ???2.32(3H,s),2.39(6H,ss),2.67(1H,dd,J=13.2Hz,

        ???J=4.9Hz),2.77(1H,dd,J=13.2Hz,J=4.9Hz),2.92

        ???(1H,d,J=4.8Hz),4.12(1H,d,J=7.4Hz),4.23(1H,

        ???d,J=8.3Hz),4.32(1H,d,J=8.3Hz),4.72(1H,s),

        ???4.92(1H,s),5.03(1H,t?like,J=4.9Hz),5.25(1H,

        ???d,J=7.4Hz),5.37(1H,d,J=10.3Hz),5.45(1H,d,

        ???J=10.3Hz),6.00(1H,d,J=4.8Hz),6.10(1H,t,J=

        ???8.3Hz),6.31(1H,d,J=3.4Hz),6.35(1H,dd,J=

        ???3.4Hz,J=2.1Hz),7.39(1H,d,J=2.1Hz),7.47(2H,

        ???t,J=7.4Hz),7.60(1H,t,J=7.4Hz),8.12(2H,d,

        ???J=7.4Hz).

        FAB质谱:853(MH+)。

        本发明实施例106

        9β-13-O-〔3-(叔丁氧基羰基氨基)-2-羟基-2-甲基-3-(2-吡啶基)丙?;?4,10-二脱乙?;?9-二氢-4-O-乙氧基羰基-9,10-O-异亚丙基浆果赤霉素III

        熔点:118-122℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.27(3H,s),1.40(3H,s),1.42(3H,t,J=7.3Hz),

        ???1.45(9H,s),1.56(3H,s),1.58(3H,s),1.64(3H,s),

        ???1.67(3H,s),2.02-2.48(4H,m),2.83(1H,d,J=

        ???4.9Hz),3.86(1H,d,J=7.8Hz),4.09(1H,br),4.12

        ???(1H,d,J=7.3Hz),4.51(3H,m),4.64(1H,d,J=

        ???7.3Hz),5.13(1H,d,J=10.3Hz),5.23(1H,br),5.51

        ???(1H,d,J=9.9Hz),6.05(2H,m),7.23(1H,m),7.45

        ???(3H,m),7.58(1H,t,J=7.3Hz),7.82(1H,t,J=

        ???6.8Hz),8.06(2H,d,J=7.3Hz),8.46(1H,m).

        FAB质谱:895(MH+)。

        本发明实施例107

        9β-4-O-丁?;?13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?4,10-二脱乙?;?9-二氢-9,10-O-〔2-(1-甲基哌嗪-4-基)亚乙基〕浆果赤霉素III

        熔点:118-128℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.02(3H,t,J=7.3Hz),1.28(3H,s),1.41(9H,s),

        ???1.61(3H,s),1.65(3H,s),1.70(3H,s),1.84(2H,m),

        ???2.03-3.07(20H,m),3.82(1H,d,J=7.3Hz),4.08

        ???(1H,br),4.36(2H,ABq,J=8.3Hz),4.70(1H,s),5.01

        ???(1H,t,J=2.8Hz),5.06(1H,s),5.20(1H,d,J=

        ???7.3Hz),5.33(2H,br),6.03(1H,d,J=4.4Hz),6.09

        ???(1H,t,J=8.2Hz),6.33(1H,d,J=2.8Hz),6.36(1H,

        ???d,J=2.4Hz),7.39(1H,s),7.48(2H,t,J=7.8Hz),

        ???7.61(1H,t,J=6.8Hz),8.12(2H,d,J=7.4Hz).

        FAB质谱:952(MH+)。

        本发明实施例108

        9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-2-羟基-3-(2-噻吩基)丙?;?4-O-乙氧基羰基-4,10-二脱乙?;?9-二氢-9,10-O-(2-吗啉代亚乙基)浆果赤霉素III

        熔点:126-130℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.24(3H,s),1.30-1.45(3H,m),1.41(3H,s),1.61

        ???(3H,s),1.64(3H,s),1.67(3H,s),1.84(1H,s),2.00-

        ???2.12(1H,m),2.17-2.30(2H,m),2.45(1H,dd,J=

        ???15.1Hz,J=9.8Hz),2.52-2.94(7H,m),3.73(4H,t

        ???like,J=4.4Hz),3.79(1H,d,J=7.3Hz),4.06(1H,

        ???br),4.13-4.46(3H,m),4.46-4.70(3H,m),5.03

        ???(1H,t,J=3.9Hz),5.16-5.27(2H,m),5.53(2H,br),

        ???5.86-6.02(1H,m),6.10(1H,d,J=4.4Hz),6.97(1H,

        ???dd,J=4.9Hz,J=3.4Hz),7.11(1H,d,J=3.4Hz),

        ???7.18-7.35(1H,m),7.44(2H,t,J=7.8Hz),7.59(1H,

        ???t,J=7.8Hz),8.04(2H,d,J=7.8Hz).

        FAB质谱:957(MH+)。

        本发明实施例109

        9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-2-羟基-3-(2-噻吩基)丙?;?4-O-乙氧基羰基-4,10-二脱乙?;?9-二氢-9,10-O-〔2-(1-甲基哌嗪-4-基)亚乙基〕浆果赤霉素III

        熔点:132-135℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.20-1.50(3H,s),1.24(3H,s),1.40(9H,s),1.60

        ???(3H,s),1.64(3H,s),1.67(3H,s),1.84(1H,s),2.00

        ???-2.10(1H,m),2.10-2.95(11H,m),2.31(3H,s),

        ???3.79(1H,d,J=7.3Hz),4.06(1H,s),4.11-4.50(3H,

        ???m),4.53(1H,d,J=8.8Hz),4.63(1H,s),5.01(1H,t,

        ???J=4.4Hz),5.21(2H,s?like),5.52(2H,br),5.84-

        ???6.02(1H,m),6.09(1H,d,J=4.9Hz),6.97(1H,dd,

        ???J=14.9Hz,J=3.9Hz),7.10(1H,d,J=3.9Hz),7.20-

        ???7.35(1H,m),7.44(2H,t,J=7.8Hz),7.59(1H,t,J=

        ???7.8Hz),8.04(2H,d,J=7.8Hz).

        FAB质谱:970(MH+)。

        本发明实施例110

        9β-13-O-〔(2R,3R)-3-(苄基氨基)-3-(2-呋喃基)-2-羟基丙?;?4-O-环丙烷羰基-4,10-二脱乙?;?9-二氢-9,10-O-(2-亚丙烯基)浆果赤霉素III

        熔点:151-153℃(由二噁烷冷冻干燥)??1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ?????1.04-1.30(2H,m),1.25(3H,s),1.30-1.55(2H,m),

        ?????1.59(3H,s),1.64(3H,s),1.67(3H,s),1.70-1.86

        ?????(1H,m),1.97(1H,s),2.03-2.32(3H,m),241(1H,

        ?????dd,J=15.1Hz,J=9.7Hz),2.90(1H,d,J=4.8Hz),

        ???3.85(1H,d,J=7.3Hz),4.07(1H,br?s),4.27(1H,d,

        ???J=8.8Hz),4.32(1H,d,J=8.8Hz),4.42(1H,br),

        ???4.57(1H,br?d,J=7.3Hz),4.79(1H,d,J=2.9Hz),

        ???5.06(1H,s),5.19(1H,d,J=6.3Hz),5.23(1H,d,J=

        ???7.3Hz),5.44(1H,d,J=10.7Hz),5.55(1H,d,J=

        ???17.6Hz),5.89-6.18(4H,m),6.36(1H,dd,J=3.4Hz,

        ???J=2.0Hz),6.39(1H,d,J=3.4Hz).

        FAB质谱:868(MH+)。

        本发明实施例111

        9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?4-O-环丙烷羰基-4,10-二脱乙?;?9-二氢-9,10-O-〔2-(1-甲基哌嗪-4-基)亚乙基〕浆果赤霉素III

        熔点:124-127℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3-CD3OD(4∶1(v/v))/TMS)δ(ppm)

        ???1.10(4H,m),1.28(3H,s),1.41(9H,s),1.57(3H,s),

        ???1.63(3H,s),1.74(3H,s),2.04-3.20(16H,m),2.70

        ???(3H,s),3.84(1H,d,J=7.8Hz),4.04(1H,br),4.39

        ???(2H,ABq,J=7.8Hz),4.72(1H,br),5.00(1H,t,J=

        ???3.6Hz),5.05(1H,s),5.23(1H,d,J=6.8Hz),5.38

        ???(1H,d,J=6.8Hz),6.03(2H,m),6.33(1H,d,J=

        ???2.8Hz),6.35(1H,t,J=2.0Hz),7.37(1H,s),7.48

        ???(2H,t,J=7.8Hz),7.61(1H,t,J=7.3Hz),8.05(2H,

        ???d,J=7.3Hz).

        FAB质谱:51(MH2+)。

        本发明实施例112

        9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?4-O-环丙烷羰基-4,10-二脱乙?;?9-二氢-9,10-O-(2-二甲基氨基亚乙基)浆果赤霉素III

        熔点:129-136℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.10(4H,m),1.28(3H,s),1.42(9H,s),1.58(3H,s),

        ???1.63(3H,s),1.75(3H,s),2.03-2.36(5H,m),2.71

        ???(3H,s),2.91(3H,s),3.12(2H,m),3.90(1H,d,J=

        ???6.8Hz),4.05(1H,m),4.30(2H,ABq,J=8.8Hz),4.72

        ???(1H,s),5.06(1H,s),5.21(1H,br),5.30(1H,d,J=

        ???6.8Hz),5.38(2H,m),6.03(2H,m),6.33(1H,d,J=

        ???2.8Hz),6.35(1H,d,J=2.0Hz),7.37(1H,s),7.49

        ???(2H,t,J=7.3Hz),7.60(1H,t,J=7.3Hz),8.04(2H,

        ???d,J=7.8Hz).

        FAB质谱:896(MH2+)。

        本发明实施例113

        9β-13-O-〔(2R,3R)-3-(苄基氨基)-3-(2-呋喃基)-2-羟基丙?;?4-O-环丙烷羰基-4,10-二脱乙?;?9-二氢-9,10-O-(2-吗啉代亚乙基)浆果赤霉素III

        熔点:148-151℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.04-1.30(2H,m),1.25(3H,s),1.34-1.53(2H,m),

        ???1.58(3H,s),1.62(3H,s),1.63(3H,s),1.72-1.84

        ???(1H,m),1.93(1H,s),2.00-2.24(3H,m),2.40(1H,

        ???dd,J=15.1Hz,J=9.8Hz),2.52-2.70(4H,m),2.73

        ???(1H,dd,J=13.2Hz,J=4.9Hz),2.81(1H,dd,J=

        ???13.2Hz,J=3.9Hz),3.66-3.83(4H,m),3.77(1H,d,

        ???J=6.8Hz),4.05-4.08(1H,m),4.27(1H,d,J=

        ???8.8Hz),4.33(1H,d,J=8.8Hz),4.66(1H,d,J=

        ???8.3Hz),4.79(1H,s?like),5.00(1H,t,J=3.9Hz),

        ???5.06(1H,s),5.17(1H,d,J=6.8Hz),5.93(1H,dd,

        ???J=9.3Hz,J=2.5Hz),6.02-6.15(2H,m),6.35(1H,

        ???d,J=1.9Hz),6.36(1H,dd,J=3.4Hz,J=1.9Hz),

        ???7.12(1H,d,J=9.3Hz),7.37(1H,s?like),7.40-7.59

        ???(5H,m),7.61(1H,t,J=7.8Hz),7.80(2H,d,J=

        ???8.3Hz),8.04(2H,d,J=8.3Hz).

        FAB质谱:941(MH+)。

        本发明实施例114

        9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?4,10-二脱乙?;?7-脱氧-4-O-乙氧基羰基-9-二氢-9,10-O-(2-吗啉代亚乙基)浆果赤霉素III

        熔点:118-119℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.25(3H,s),1.37(3H,t,J=5.8Hz),1.41(9H,s),

        ???1.49(3H,s),1.50-2.10(4H,m),1.60(3H,s),1.77

        ???(3H,s),1.85(1H,s),2.20(1H,dd,=15.3Hz,J=

        ???3.4Hz),2.45(1H,dd,J=15.3Hz,J=9.3Hz),2.52?

        ???2.94(7H,m),3.74(4H,t,J=4.4Hz),4.02(1H,br),

        ???4.11(1H,d,J=7.3Hz),4.22(1H,d,J=8.8Hz),

        ???4.25-4.57(3H,m),4.71(1H,s),5.00(1H,s),5.05

        ???(1H,t,J=8.9Hz),5.26(1H,d,J=7.3Hz),5.35

        ???(1H,d,J=10.2Hz),5.41(1H,d,J=10.2Hz),5.97

        ???(1H,t,J=7.3Hz),6.04(1H,d,J=4.4Hz),6.25-

        ???6.40(2H,m),7.38(1H,s),7.44(2H,t,J=7.8Hz),

        ???7.59(1H,t,J=7.8Hz),8.07(2H,d,J=7.8Hz).

        FAB质谱:925(MH+)。

        本发明买施例115

        9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?4,10-二脱乙?;?7-脱氧-4-O-乙氧基羰基-9-二氢-9,10-O-(2-甲基氨基亚乙基)浆果赤霉素III

        熔点:114-115℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.25(3H,s),1.36(3H,t,J=6.9Hz),1.41(9H,s),

        ???1.49(3H,s),1.50-2.30(6H,m),1.61(3H,s),1.78

        ???(3H,s),2.35-2.51(1H,m),2.39(6H,m),2.67(1H,

        ???dd,J=13.2Hz,J=5.4Hz),2.76(1H,dd,J=13.2Hz,

        ???J=3.9Hz),2.85(1H,d,J=4.9Hz),4.11(1H,d,J=

        ???7.3Hz),4.22(1H,d,J=8.8Hz),4.23-4.57(3H,m),

        ???4.71(1H,5),4.95-5.08(2H,m),5.27(1H,d,J=

        ???7.3Hz),5.35(1H,d,J=8.8Hz),5.42(1H,d,J=

        ???8.8Hz),5.98(1H,t,J=7.8Hz),6.04(1H,d,J=

        ???4.9Hz),6.23-6.39(2H,m),7.38(1H,s),7.44(2H,

        ???t,J=7.8Hz),7.60(1H,t,J=7.8Hz),8.07(2H,d,

        ???J=7.8Hz).

        FAB质谱:883(MH+)。

        本发明实施例116

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?10-脱乙?;?7-脱氧-6,7-二脱氢-9-二氢-9,10-O-(2-亚丙烯基)浆果赤霉素III

        熔点:148-151℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.24(3H,s),1.40(9H,br?s),1.52(3H,s),1.58(3H,

        ???s),1.59(3H,s),1.84-(1H,s),2.14(1H,dd,J=7.8,

        ???15.1Hz),2.33(3H,s),2.44(1H,dd,J=9.9,15.1Hz),

        ???3.08(1H,d,J=5.9Hz),3.97(1H,d,J=7.3Hz),4.07

        ???-4.16(1H,br?s),4.24(1H,d,J=8.1Hz),4.34(1H,

        ???d,J=8.1Hz),4.63(1H,br?s),4.86(1H,br?d,J=

        ???4.2Hz),5.22(1H,d,J=7.3Hz),5.26(1H,d,J=

        ???6.4Hz),5.30(1H,br?d,J=8.8Hz),5.49(1H,d,J=

        ???10.7Hz),5.61(1H,d,J=17.1Hz),5.52-5.63(1H,m),

        ???5.70(1H,dd,J=10.3,4.2Hz),5.97-6.10(3H,m),

        ???6.11(1H,d,J=10.3Hz),7.25-7.43(5H,m),7.48

        ???(2H,t,J=7.5Hz),7.61(1H,t,J=7.5Hz),8.13(2H,

        ???d,J=7.5Hz).

        FAB质谱:830(MH+)。

        本发明实施例117

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?10-脱乙?;?7-脱氧-6,7-二脱氢-9-二氢-9,10-O-(2-吗啉代亚乙基)浆果赤霉素III

        熔点:150-153℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.23(3H,s),1.39(9H,s),1.51(3H,s),1.57(3H,s),

        ???1.64(3H,br?s),1.84(1H,s),2.15(1H,dd,J=7.3,

        ???14.8Hz),2.32(3H,s),2.39(1H,dd,J=9.5,14.8Hz),

        ???2.55-2.70(4H,m),2.75(1H,dd,J=4.9,13.7Hz),

        ???2.82(1H,dd,J=3.9,13.7Hz),3.07(1H,d,J=

        ???5.9Hz),3.74(4H,t,J=4.6Hz),3.91(1H,d,J=

        ???7.6Hz),4.00-4.15(1H,br?s),4.24(1H,d,J=

        ???7.8Hz),4.34(1H,d,J=7.8Hz),4.63(1H,br?s),4.85

        ???(1H,d,J=4.2Hz),5.05(1H,dd,J=3.9,4.9Hz),5.15

        ???(1H,d,J=7.6Hz),5.30(1H,br?d,J=9.3Hz),5.62

        ???(1H,br?d,J=9.3Hz),5.69(1H,dd,J=10.3,4.2Hz),

        ???5.96(1H,d,J=5.9Hz),6.03-6.09(1H,m),6.07(1H,

        ???d,J=10.3Hz),7.30-7.43(5H,m),7.49(2H,t,J=

        ???7.3Hz),7.61(1H,t,J=7.3Hz),8.13(2H,d,J=

        ???7.3Hz).

        本发明实施例118

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-(4-吡啶基)丙?;?10-脱乙?;?7-脱氧-6,7-二脱氢-9-二氢-9,10-O-异亚丙基浆果赤霉素III

        熔点:162-165℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.22(3H,s),1.41(9H,s),1.42(3H,s),1.52(3H,s),

        ???1.53(3H,s),1.57(3H,s),1.60(3H,s),1.86(1H,s),

        ???2.34(3H,s),2.05-2.17(1H,m),2.32-2.43(1H,m),

        ???3.07(1H,d,J=5.7Hz),3.97(1H,d,J=7.3Hz),4.22

        ???(1H,d,J=7.8Hz),4.37(1H,d,J=7.8Hz),4.39(1H,

        ???br?s),4.63(1H,br?s),4.86(1H,d,J=4.0Hz),5.32

        ???(1H,br?d,J=9.6Hz),5.47(1H,d,J=7.3Hz),5.69

        ???(1H,dd,J=4.0,10.3Hz),5.73(1H,br?d,J=9.6Hz),

        ???5.98(1H,d,J=5.7Hz),6.10(1H,d,J=10.3Hz),6.02

        ???-6.14(1H,br),7.36(2H,d,J=5.9Hz),7.48(2H,t,

        ???J=7.4Hz),7.61(1H,t,J=7.4Hz),8.14(2H,d,J=

        ???7.4Hz),8.60(2H,d,J=5.9Hz).

        FAB质谱:833(MH+)。

        本发明实施例119

        9β-4-O-丁?;?13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?7-脱氧-4,10-二脱乙?;?6,7-二脱氢-9-二氢-9,10-O-(2-亚丙烯基)浆果赤霉素III

        熔点:127-130℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.23-1.29(3H,m),1.41(9H,s),1.53(3H,s),1.60

        ???(6H,s),1.70(3H,s),1.77-1.92(2H,m),2.27(1H,

        ???dd,J=8.3,15.3Hz),2.39(1H,dd,J=9.5,15.3Hz),

        ???2.44-2.70(2H,m),3.12(1H,d,J=5.9Hz),3.76(1H,

        ???br?s),4.01(1H,d,J=7.3Hz),4.27(1H,d,J=8.3Hz),

        ???4.34(1H,d,J=8.3Hz),4.71(1H,br?d,J=3.9Hz),

        ???4.81(1H,d,J=4.2Hz),5.22(1H,d,J=7.3Hz),5.25

        ???(1H,d,J=6.4Hz),5.33(2H,br?s),5.48(1H,d,J=

        ???10.7Hz),5.60(1H,d,J=17.1Hz),5.70(1H,dd,J=

        ???10.3,4.2Hz),5.99(1H,d,J=5.9Hz),6.00-6.13(2H,

        ???m),6.12(1H,d,J=10.3Hz),6.34(1H,d,J=2.9Hz),

        ???6.35-6.38(1H,m),7.40(1H,br?s),7.49(2H,t,J=

        ???7.3Hz),7.62(1H,t,J=7.3Hz),8.16(2H,d,J=

        ???7.3Hz)

        本发明实施例120

        9β-4-O-丁?;?13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?7-脱氧-4,10-二脱乙?;?6,7-二脱氢-9-二氢-9,10-O-(2-吗啉代亚乙基)浆果赤霉素III

        熔点:132-135℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.01(3H,t,J=7.3Hz),1.25(3H,s),1.40(9H,s),????

        ???1.52(3H,s),1.56(3H,s),1.68(3H,s),1.78-1.90

        ???(2H,m),2.28(1H,dd,J=8.3,14.9Hz),2.39(1H,dd,

        ???J=9.5,14.9Hz),2.44-2.55(1H,m),2.55-2.70(5H,

        ???m),2.76(1H,dd,J=13.7,5.1Hz),2.81(1H,dd,J=

        ???13.7,3.9Hz),3.10(1H,d,J=6.2Hz),3.75(4H,t,J=

        ???4.7Hz),3.97(1H,d,J=7.5Hz),4.26(1H,d,J=

        ???8.3Hz),4.33(1H,d,J=8.3Hz),4.71(1H,br?s),4.81

        ???(1H,d,J=3.9Hz),5.04(1H,dd,J=5.1,3.9Hz),5.16

        ???(1H,d,J=7.5Hz),5.32(2H,br?s),5.70(1H,dd,J=

        ???10.3,3.9Hz),5.96(1H,d,J=6.2Hz),6.03-6.13(1H,

        ???m),6.09(1H,d,J=10.3Hz),6.30-6.40(2H,m),7.40

        ???(1H,s),7.50(2H,t,J=7.3Hz),7.62(1H,t,J=

        ???7.3Hz),8.16(2H,d,J=7.3Hz).

        本发明实施例121

        9β-13-O-〔3-(叔丁氧基羰基氨基)-2-羟基-2-甲基-3-(4-吡啶基)丙?;?4-O-环丙烷羰基-7-脱氧-4,10-二脱乙?;?6,7-二脱氢-9-二氢-9,10-O-异亚丙基浆果赤霉素III

        熔点:165-168℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDC13/TMS)δ(ppm)

        ???1.25(s),1.38(s),1.42(s),1.51(s),1.57(s),1.59

        ???(s),2.20(1H,m),2.28(1H,m),3.11(1H,d,J=5Hz),

        ???3.94(1H,d,J=7.5Hz),4.14(1H,d,J=8Hz),4.33

        ???(1H,d,J=8Hz),4.54(1H,br),4.75(1H,d,J=4Hz),

        ???5.00(1H,d,J=9.5Hz),5.45(1H,d,J=7.5Hz),5.67

        ???(1H,dd,J=10Hz,4Hz),5.85(1H,d,J=9.5Hz),6.00

        ???(1H,d,J=5Hz),6.07(1H,d,J=10Hz),6.18(1H,t-

        ???br),7.34(2H,d,J=5.5Hz),7.50(2H,t,J=7.5Hz),

        ???7.62(1H,t,J=7.5Hz),8.07(2H,d,J=7.5Hz),8.57

        ???(2H,d,J=5.5Hz).

        FAB质谱:873(M+)。

        本发明实施例122

        9β-13-O-〔3-(叔丁氧基羰基氨基)-2-羟基-2-甲基-3-(4-吡啶基)丙?;?10-脱乙?;?7-脱氧-6,7-二脱氢-9-二氢-9,10-O-异亚丙基浆果赤霉素III

        熔点:161-164℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.27(s),1.34(9H,s),1.42(s),1.54(s),1.58(s),

        ???1.59(s),2.22(2H,m),2.52(3H,s),3.10(1H,d,J=

        ???5.5Hz),3.98(1H,d,J=7.5Hz),4.24(1H,d,J=8Hz),

        ???4.38(1H,d,J=8Hz),4.85(1H,d,J=4Hz),5.02(1H,

        ???d,J=10Hz),5.44(1H,d,J=7.5Hz),5.69(1H,dd,J

        ???=10Hz,4Hz),5.74(1H,d,J=10Hz),5.96(1H,d,J=

        ???5.5Hz),6.10(1H,d,J=10Hz),6.23(1H,t,J=9Hz),

        ???7.35(2H,d,J=5Hz),7.49(2H,t,J=7.5Hz),7.61(

        ???1H,t,J=7.5Hz),8.15(2H,d,J=7.5Hz),8.60(2H,

        ???d,J=5Hz).

        FAB质谱:847(M+)。

        本发明实施例123

        9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?4-O-环丙烷羰基-7-脱氧-4,10-二脱乙?;?6,7-二脱氢-9-二氢-9,10-O-(2-吗啉代亚乙基)浆果赤霉素III

        熔点:105-110℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.25(7H,s?like),1.41(9H,s),1.50(3H,s),1.56

        ???(3H,s),1.71(3H,s),2.33-2.44(3H,m),2.64(4H,

        ???m),2.79(2H,ABq,J=8.3Hz),3.10(1H,d,J=5.9Hz),

        ???3.72-7.76(4H,m),3.94(1H,d,J=7.3Hz),4.25(2H,

        ???ABq,J=8.3Hz),4.73(1H,s),4.78(1H,d,J=4.4Hz),

        ???5.05(1H,dd,J=4.9Hz,3.9Hz),5.45(1H,d,J=

        ???17.2Hz),5.69(1H,dd,10.3Hz,3.9Hz)5.98(1H,d,J=

        ???5.9Hz),6.04(1H,m),6.07(1H,d,J=10.7Hz),6.32

        ???(1H,d,J=3.4Hz),6.35(1H,dd,J=3.4Hz,2.0Hz),

        ???7.36(1H,s),7.50(2H,t,J=7.3Hz),7.62(1H,t,J=

        ???7.3Hz),8.10(2H,d,J=7.3Hz).

        FAB质谱:919(MH+)。

        本发明实施例124

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-(2-吡啶基)丙?;?10-脱乙?;?7-脱氧-6,7-二脱氢-9-二氢-9,10-O-异亚丙基浆果赤霉素III

        熔点:143-148℃(由二噁烷冷冻干燥)1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.24(3H,s),1.41(3H,s),1.43(9H,s),1.55(3H,s),

        ???1.59(3H,s),1.60(3H,s),1.66(3H,s),1.80(1H,s),

        ???2.23-2.38(2H,m),2.42(3H,s),3.12(1H,d,J=

        ???5.9Hz),4.06(1H,d,J=7.6Hz),4.28(1H,?d,J=

        ???8.3Hz),4.33(1H,d,J=8.3Hz),4.78(1H,br?s),4.87

        ???(1H,br?s),4.88(1H,d,J=4.2Hz),5.35(1H,br?d,

        ???J=9.8Hz),5.47(1H,d,J=7.8Hz),5.68(1H,dd,J=

        ???4.2,10.6Hz),5.91(1H,d,J=9.8Hz),5.94(1H,d,J=

        ???5.9Hz),6.09(1H,d,J=10.6Hz),6.05-6.15(1H,m),

        ???7.20-7.28(1H,m),7.41(1H,d,J=7.8Hz),7.48(2H,

        ???t,J=7.3Hz),7.60(1H,t,J=7.3Hz),7.73(1H,d,

        ???J=7.8Hz),8.14(2H,d,J=7.3Hz),8.52(1H,d,J=

        ???4.4Hz).

        本发明实施例125

        9β-4-O-丁?;?13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?7-脱氧-4,10-二脱乙?;?9-二氢-7β,8β-亚甲基-9,10-O-(2-吗啉代亚乙基)-19-降浆果赤霉素III1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.74(1H,br?t,J=5.0Hz),0.99(3H,t,J=7.6Hz),

        ???1.18-1.80(9H,m),1.20(3H,s),1.35(9H,s),1.53

        ???(3H,s),2.29(1H,dd,J=8.8Hz,15.6Hz),2.40-2.77

        ???(10H,m),3.12(1H,d,J=8.3Hz),3.36(1H,br?s),

        ???3.72(4H,t,J=4.6Hz),4.13(1H,dd,J=7.8Hz,

        ???2.6Hz),4.32(1H,d,J=7.8Hz),4.47-4.55(2H,m),

        ???4.67(1H,br?s),4.91(1H,t,J=4.4Hz),5.09(1H,

        ???d,J=7.3Hz),5.24(1H,d,J=9.7Hz),5.38(1H,br

        ???d,J=9.7Hz),5.52(1H,d,J=8.3Hz),6.22(1H,br

        ???t,J=8.8Hz),6.35(1H,d,J=2.9Hz),6.39(1H,dd,

        ???J=2.9Hz,1.5Hz),7.42(1H,d,J=1.5Hz),7.49(2H,

        ???t,J=7.8Hz),7.57(1H,t,J=7.8Hz),8.08(2H,d,

        ???J=7.8Hz).

        本发明实施例126

        9β-13-O-〔(2R,3S)-3-(叔丁氧基羰基氨基)-2-羟基-3-苯基丙?;?10-脱乙?;?7-脱氧-9-二氢-7β,8β-亚甲基-9,10-O-(2-吗啉代亚乙基)-19-降浆果赤霉素III1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.77(1H,br?s),1.10-1.80(3H,m),1.21(3H,s),

        ???1.34(9H,s),1.54(3H,s),1.68(9H,s),1.75(1H,

        ???s),2.23(3H,s),2.31(1H,dd,J=8.8Hz,15.6Hz),

        ???2.50-2.78(8H,m),3.12(1H,d,J=8.3Hz),3.48

        ???(1H,br?s),3.65-3.78(4H,m),4.17(1H,dd,J=

        ???7.8Hz,2.0Hz),4.32-4.48(2H,m),4.54(1H,t,J=

        ???8.8Hz),4.60(1H,br?s),4.91(1H,t,J=4.2Hz),

        ???5.09(1H,d,J=7.3Hz),5.31(1H,br?d,J=9.1Hz),

        ???5.47(1H,d,J=9.1Hz),5.53(1H,d,J=8.3Hz),

        ???6.20(1H,br?t,J=8.3Hz),7.30-7.43(5H,m),7.49

        ???(2H,t,J=7.8Hz),7.57(1H,t,J=7.8Hz),8.08

        ???(2H,d,J=7.8Hz).参考例1步骤1:9β-10-脱乙?;?13-脱氧-9-二氢-9,10-O-异亚丙基-13-氧代浆果赤霉素III

        将0.1301g本发明实施例1步骤2中所得化合物溶于6.5ml二噁烷中,于室温将该溶液与0.823g二氧化锰混合并在室温下剧烈搅拌15小时。用硅藻土过滤该反应混合物,用氯仿洗涤该滤过的物料,然后在减压下蒸发该所得滤液中的溶剂。之后用硅胶薄层色谱法(展开溶剂:氯仿∶丙酮=10∶1(v/v)),则得到0.1154g呈无色透明浆状标题化合物。Rf=0.60(氯仿∶丙酮=10∶1(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.27(3H,s),1.43(3H,s),1.61(3H,s),1.66(3H,

        ???s),1.68(3H,s),1.94(3H,s),2.01(1H,s),2.17

        ???(2H,m),2.22(3H,s),2.64(1H,AB?type?d,J=

        ???20.0Hz),2.90(1H,AB?type?d,J=20.0Hz),3.15(1H,

        ???d,J=4.4Hz),3.99(1H,d,J=7.3Hz),4.07(1H,m),

        ???4.24(1H,AB?type?d,J=7.8Hz),4.65(1H,AB?type?d,

        ???J=7.8Hz),4.41(1H,dd,J=1.5Hz,8.8Hz),5.04

        ???(1H,s),5.68(1H,d,J=7.3Hz),6.16(1H,d,J=

        ???4.8Hz),7.49(2H,t,J=7.8Hz),7.60(1H,t,J=

        ???7.8Hz),8.11(2H,d,J=7.8Hz).步骤2:9β-10-脱乙?;?13-脱氧-9-二氢-9,10-O-异亚丙基-13-氧代-7-O-三乙基甲硅烷基浆果赤霉素III

        于-32℃下将上述步骤1所得的73.0mg化合物溶于2.2ml二氯甲烷中,将该溶液与0.075ml?2,6-卢剔啶和0.112ml三氟甲磺酸三乙基甲硅烷基酯混合。30分钟后,于-30℃下将该溶液与饱和碳酸氢钠水液混合并用氯仿萃取,用饱和盐水洗涤该萃取液并经无水硫酸钠干燥。之后,在减压下蒸发溶剂并用硅胶柱色谱法(展开溶剂:氯仿∶甲醇=8.5∶1(v/v))纯化所得残余物,则得到48.3mg呈白色固体的标题化合物。Rf=0.40(己烷∶乙酸乙酯=7∶1(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.60(6H,q,J=7.8Hz),0.95(9H,t,J=7.8Hz),

        ???1.24(3H,s),1.44(3H,s),1.54(3H,s),1.61(3H,

        ???s),1.67(3H,s),1.94(3H,s),2.21(3H,s),1.98-

        ???2.13(2H,m),2.62(1H,AB?type?d,J=20.0Hz),2.93

        ???(1H,AB?type?d,J=20.0Hz),3.23(1H,d,J=5.4Hz),

        ???4.07(1H,t,J=2.9Hz),4.21(1H,AB?type?d,J=

        ???7.8Hz),4.43(1H,AB?type?d,J=7.8Hz),4.30(1H,

        ???br-d),4.78(1H,t,J=4.0Hz),5.61(1H,d,J=

        ???7.8Hz),6.07(1H,d,J=5.4Hz),6.94(1H,d,J=

        ???7.8Hz),7.49(2H,t,J=7.8Hz),7.60(1H,t,J=

        ???7.8Hz),8.12(2H,d,J=7.8Hz).步骤3:9β-10-脱乙?;?9-二氢-9,10-O-异亚丙基-7-O-三乙基甲硅烷基浆果赤霉素III

        将上述步骤2所得的48.3mg化合物于室温溶于四氢呋喃-甲醇(20∶1(v/v))混合溶剂中,然后将该溶液与11.0mg氢硼化钠混合。1.5小时后,通过在0℃加入饱和氯化铵水液中和该溶液并用乙酸乙酯萃取。用饱和盐水洗涤该萃取液并经无水硫酸钠干燥。在减压下蒸发溶剂后,将48.3mg所得残余物溶于2.5ml二氯甲烷中,随后于-82℃向其中滴加1.0N二异丁基氢化铝(甲苯溶液,0.17ml),之后搅拌10分钟。于-78℃将甲醇倒入该反应混合物中,在室温下向其中加入罗谢尔盐(0.23g)的水溶液(1.5ml水),并剧烈搅拌该混合物1小时。在用氯仿萃取之后,用饱和盐水洗涤所得萃取液并经无水硫酸钠干燥。之后在减压下蒸发溶剂并用硅胶薄层色谱法(展开溶剂:己烷∶乙酸乙酯=2∶1(v/v))纯化所得残余物,则得到10.8g呈无色透明浆状的标题化合物。Rf=0.49(己烷∶乙酸乙酯=2∶1(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.61(6H,q,J=7.8Hz),0.95(9H,t,J=7.8Hz),

        ???1.12(3H,s),1.40(3H,s),1.49(3H,s),1.56(3H,

        ???s),1.57(3H,s),1.93(3H,s),1.95-2.11(3H,m),

        ???2.26-2.44(2H,m),2.32(3H,s),3.16(1H,d,J=

        ???4.9Hz),4.06(1H,t,J=4.8Hz),4.21(1H,AB?type?d,

        ???J=7.8Hz),4.54(1H,AB?type?d,J=7.8Hz),4.72-

        ???4.84(2H,m),5.51(1H,d,J=7.8Hz),5.91(1H,d,

        ???J=4.9Hz),7.48(2H,t,J=7.3Hz),7.59(1H,t,J=

        ???7.3Hz),8.13(2H,d,J=7.3Hz).步骤4:9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-(三异丙基甲硅烷氧基)丙?;?10-脱乙?;?9-二氢-9,10-O-异亚丙基-7-O-三乙基甲硅烷基浆果赤霉素III

        按照本发明实施例1步骤3的反应过程进行上述步骤3所得化合物与(3R,4R)-1-(叔丁氧基羰基)-4-(2-呋喃基)-3-(三异丙基甲硅烷氧基)氮杂环丁-2-酮的反应及纯化,则得到标题化合物。Rf=0.25(己烷∶乙酸乙酯=6∶1(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.62(6H,q,J=7.8Hz),0.85-1.01(30H,m),1.06

        ???(3H,s),1.23(3H,s),1.38(9H,s),1.46(6H,s),

        ???1.50(3H,s),1.76(3H,s),2.04-2.29(3H,m),2.43

        ???(3H,s),2.36-2.45(1H,m),3.16(1H,d,J=

        ???5.4Hz),3.98(1H,dd,J=8.4Hz,3.2Hz),4.25(1H,d,

        ???J=8.0Hz),4.40-4.48(1H,m),4.50(1H,d,J=

        ???8.0Hz),4.83(1H,t,J=6.8Hz),4.96(1H,s),5.25-

        ???5.36(2H,m),5.41(1H,d,J=4.8Hz),5.89(1H,d,

        ???J=5.4Hz),6.12(1H,t),6.24(1H,d,J=3.2Hz),

        ???6.34(1H,d,J=3.2Hz),7.36(1H,s),7.48(2H,t,

        ???J=7.2Hz),7.57(1H,t,J=7.2Hz),8.11(2H,d,J=

        ???7.2Hz).步骤5:9β-13-O-〔(2R,3R)-3-(叔丁氧基羰基氨基)-3-(2-呋喃基)-2-羟基丙?;?10-脱乙?;?9-二氢-9,10-O-异亚丙基浆果赤霉素III

        按本发明实施例1步骤4所述相同方式进行上述步骤3所得化合物的反应,则得到与本发明实施例1步骤4所得相同的标题化合物。参考例29β-4-O-丁?;?4,10-二脱乙?;?13-脱氧-9-二氢-9,10-O-异亚丙基-13-O-氧代浆果赤霉素III

        将84.9mg参考例1所得化合物于-58℃溶于2.9ml四氢呋喃中,向其中滴加0.73ml?1N六甲基二硅杂叠氮化钠(四氢呋喃溶液),5分钟之后加入0.058ml乙基碘。1.5小时后,于-52℃将其与饱和氯化铵水液混合,并用乙酸乙酯萃取。用饱和盐水洗涤所得萃取液并经无水硫酸钠干燥。之后,在减压下蒸发溶剂并用硅胶薄层色谱法(展开溶剂:己烷∶乙酸乙酯=5∶2(v/v))纯化所得残余物,则得到19.1g呈无色透明浆状标题化合物。Rf=0.23(己烷∶乙酸乙酯=5∶2(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.06(3H,t,J=7.3Hz),1.26(3H,s),1.43(3H,s),

        ???1.61(3H,s),1.67(3H,s),1.68(3H,s),1.68-1.80

        ???(2H,m),1.93(3H,s),1.97(1H,s),2.12-2.23(2H,

        ???m),2.38-2.54(2H,m),2.62(1H,AB?type?d,J=

        ???19.5Hz),2.89(1H,AB?type?d,J=19.5Hz),3.17(1H,

        ???d,J=4.4Hz),3.99(1H,d,J=7.3Hz),4.05-4.11

        ???(1H,m),4.24(1H,AB?type?d,J=8.8Hz),4.67(1H,

        ???type?AB?d,J=8.8Hz),4.42(1H,dd,J=8.3Hz,

        ???0.9Hz),5.00(1H,s),5.67(1H,d,J=7.3Hz),6.15

        ???(1H,d,J=4.4Hz),7.49(2H,t,J=8.3Hz),7.62

        ???(1H,t,J=8.3Hz),8.11(2H,d,J=8.3Hz).参考例39β-4-O-丁?;?4,10-二脱乙?;?13-脱氧-9-二氢-9,10-O-异亚丙基-13-氧代-7-O-三乙基甲硅烷基浆果赤霉素III

        用参考例1步骤2所得化合物,重复参考例2的反应过程,则得到呈无色透明浆状标题化合物。Rf=0.33(己烷∶乙酸乙酯=4∶1(v/v))1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.60(6H,q,J=8.0Hz),0.94(9H,t,J=8.0Hz),

        ???1.05(3H,t,J=7.6Hz),1.22(3H,s),1.43(3H,s),

        ???1.53(3H,s),1.61(3H,s),1.65(3H,s),1.66-1.82

        ???(2H,m),1.93(3H,s),1.98-2.13(2H,m),2.32-

        ???2.53(2H,m),2.59(1H,AB?type?d,J=19.5Hz),2.91

        ???(1H,AB?type?d,J=19.5Hz),3.22(1H,d,J=4.8Hz),

        ???4.08(1H,t,J=4.0Hz),4.21(1H,AB?type?d,J=

        ???7.7Hz),4.44(1H,AB?total?d,J=7.7Hz),4.24-4.35

        ???(1H,m),4.74(1H,t,J=4.0Hz),5.61(1H,d,J=

        ???7.5Hz),6.07(1H,d,J=4.8Hz),7.48(2H,t,J=

        ???7.7Hz),7.61(1H,t,J=7.7Hz),8.13(2H,d,J=

        ???7.7Hz).FAB质谱:838(MH+)。参考例4步骤1:13-O-苄氧基羰基-10-脱乙?;?7,10-双-O-(2,2,2-三氯乙氧基羰基)浆果赤霉素III

        将2.409g?10-脱乙?;?7,10-双-O-(2,2,2-三氯乙氧基羰基)浆果赤霉素III溶于15ml无水四氢呋喃中,向其中滴加0.92g冷至-50℃的苄氧基碳酰氯。然后向其中滴加5.38ml?1N六甲基二硅杂叠氮化钠(四氢呋喃溶液),随后于相同温度下搅拌3小时。将该反应溶液与氯化铵水液混合并用乙酸乙酯萃取。用饱和盐水洗涤所得萃取液并经无水硫酸钠干燥。之后,在减压下蒸发溶剂,并用硅胶柱色谱法(展开溶剂含10%(v/v)乙酸乙酯的己烷,然后变至15%和20%)纯化所得残余物,则得到呈无色玻璃状固体的1.607g标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.18(3H,s),1.19(3H,s),1.84(3H,s),2.0-2.2

        ???(1H,m),2.06(1H,d,J=1Hz),2.28(3H,s),2.35

        ???(2H,m),2.62(1H,ddd,J=15Hz,9Hz,7Hz),3.94

        ???(1H,d,J=7Hz),4.13(1H,d,J=8Hz),4.32(1H,d,

        ???J=8Hz),4.60(1H,d,J=12Hz),4.76(1H,AB?type

        ???d,J=12Hz),4.79(1H,AB?type?d,J=12Hz),4.91

        ???(1H,d,J=12Hz),4.96(1H,d,J=8Hz),5.25(2H,

        ???s),5.60(1H,dd,J=11Hz,7Hz),5.66(1H,d,J=

        ???7Hz),5.95(1H,t,J=8Hz),6.26(1H,s),7.40(5H,

        ???s),7.48(2H,t,J=7.5Hz),7.62(1H,t,J=7.5Hz),

        ???8.07(2H,m).步骤2:13-O-苄氧基羰基-10-脱乙?;嗝顾豂II

        按照本发明实施例9步骤3所述相同方式进行上述步骤1所得化合物的反应,则得到标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.11(3H,s),1.16(3H,s),1.74(3H,s),1.82(1H,

        ???m),1.97(3H,s),2.25(3H,s),2.32(2H,m),2.59

        ???(1H,ddd,J=14Hz,9.5Hz,6.5Hz),3.96(1H,d,J=

        ???7Hz),4.16(2H,m),4.30(2H,m),4.95(1H,d,J=

        ???8Hz),5.24(3H,m),5.65(1H,d,J=7Hz),5.92(1H,

        ???t,J=8Hz),7.40(5H,s),7.48(2H,t,J=7.5Hz),

        ???7.62(1H,t,J=7.5Hz),8.07(2H,m).步骤3:9β-13-O-苄氧基羰基-10-脱乙?;?9-二氢浆果赤霉素III

        于室温下将上述步骤2所得119mg化合物溶于10ml无水二氯甲烷中,将该溶液与180mg四丁基氢硼化铵混合并于室温搅拌15小时。将该反应溶液与1N盐酸混合并搅拌直至不起泡。收集有机层,用饱和盐水洗涤然后用无水硫酸钠干燥。在减压下蒸发溶剂,并将所得残余物溶于甲醇中再静置3小时。之后在减压下蒸发溶剂并用硅胶薄层色谱法(展开溶剂:含6%(v/v)甲醇的氯仿)纯化所得残余物,则得到呈白色粉状的86mg标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.25(3H,s),1.64(3H,s),1.75(3H,s),1.80(3H,

        ???s),1.91(1H,m),2.19(3H,s),2.29(2H,m),2.49

        ???(1H,m),3.08(1H,d,J=5Hz),4.11(1H,br),4.16

        ???(1H,d,J=8Hz),4.34(2H,m),4.98(1H,d,J=

        ???7Hz),5.17(2H,d?and?br,J=12Hz),5.27(1H,d,J=

        ???12Hz),5.96(1H,t,J=8Hz),6.09(1H,d,J=5Hz),

        ???7.39(5H,m),7.46(2H,t,J=7.5Hz),7.58(1H,t,

        ???J=7.5Hz),8.08(2H,d,J=7.5Hz).步骤4:9β-13-O-苄氧基羰基-10-脱乙?;?9-二氢-9,10-O-异亚丙基浆果赤霉素III

        按本发明实施例1步骤2所述相同方式进行上述步骤3所得化合物的反应,则得到呈玻璃状固体的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.23(3H,s),1.40(3H,s),1.57(3H,s),1.63(3H,

        ???s),1.65(3H,s),1.79(3H,s),2.18(2H,m),2.23

        ???(3H,s),2.30(2H,m),2.97(1H,d,J=5Hz),3.89

        ???(1H,d,J=7.5Hz),4.03(1H,m),4.26(1H,d,J=

        ???8Hz),4.38(1H,d,J=8Hz),4.66(1H,d,J=8Hz),

        ???5.09(1H,br),5.18(1H,d,J=12Hz),5.26(1H,d,

        ???J=12Hz),5.55(1H,d,J=7.5Hz),5.92(1H,t,J=

        ???8Hz),5.99(1H,d,J=5Hz),7.39(5H,m),7.46(2H,

        ???t,J=7.5Hz),7.59(1H,t,J=7.5Hz),8.09(2H,d,

        ???J=7.5Hz).步骤5:9β-13-O-苄氧基羰基-10-脱乙?;?9-二氢-9,10-O-异亚丙基-7-O-三乙基甲硅烷基浆果赤霉素III

        按本发明实施例3步骤2所述相同方式进行上述步骤3所得化合物的反应,则得到呈玻璃状固体的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.62(6H,q,J=8Hz),0.97(9H,t,J=7Hz),1.15

        ???(3H,s),1.38(3H,s),1.47(3H,s),1.51(3H,s),

        ???1.79(3H,d,J=1Hz),2.08(1H,m),2.24(3H,s),

        ???2.28-2.39(3H,m),3.21(1H,d,J=6Hz),3.94

        ???(1H,dd,J=10Hz,4Hz),4.27(1H,d,J=8Hz),4.46

        ???(1H,d,J=8Hz),4.54(1H,br),4.80(1H,t,J=

        ???7Hz),5.19(1H,d,J=12Hz),5.25(1H,d,J=12Hz),

        ???5.42(1H,d,J=9Hz),5.84(1H,d,J=6Hz),5.88

        ???(1H,t,J=10Hz),7.39(5H,m),7.46(2H,t,J=

        ???7.5Hz),7.59(1H,t,J=7.5Hz),8.08(2H,d,J=

        ???7.5Hz).步骤6:9β-10-脱乙?;?9-二氢-9,10-O-异亚丙基-7-O-三乙基甲硅烷基浆果赤霉素III

        将122mg上述步骤5所得化合物溶于10ml甲醇中,再将该溶液与40mg?10%钯-碳混合并在氢气氛下搅拌1小时。过滤去除不溶物,在减压下蒸发所得滤液中的溶剂。有硅胶薄层色谱法(展开溶剂:含5%(v/v)丙酮的氯仿)纯化所得残余物,则得到80mg与本发明实施例3步骤3所得相同的标题化合物。参考例59β-10-脱乙?;?9-二氢-9,10-O-(2-亚丙烯基)-7-O-三乙基甲硅烷基浆果赤霉素III

        将0.4030g?9β-10-脱乙?;?9-二氢-9,10-O-(2-亚丙烯基)浆果赤霉素III溶于80ml二氯甲烷中,在室温下将该溶液与0.232ml?2,6-二-叔丁基吡啶混合,然后冷至-78℃。向其中滴加0.202ml三氟甲磺酸三乙基甲硅烷基酯。16分钟后,于-78℃将该溶液与甲醇和饱和碳酸氢钠水液混合,用氯仿萃取。用饱和盐水洗涤该萃取液并经无水硫酸钠干燥。之后,在减压下蒸发溶剂并用硅胶柱色谱法(展开溶剂:己烷∶乙酸乙酯=20∶1(v/v)→氯仿∶丙酮=7∶1(v/v))纯化所得残余物,则得到0.4126g的呈白色泡沫状的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.58-0.71(6H,m),0.98(9H,t,J=7.8Hz),1.09(3H,

        ???s),1.56(3H,s),1.60(3H,s),1.75(1H,s),1.94(3H,

        ???s),2.00-2.45(4H,m),2.30(3H,s),3.19(1H,d,J=

        ???5.3Hz),3.95(1H,dd,J=8.8Hz,J=5.8Hz),4.32(1H,

        ???d,J=8.3Hz),4.35(1H,d,J=8.3Hz),4.61(1H,d,

        ???J=7.8Hz),4.72-4.89(2H,m),5.09(1H,d,J=

        ???5.8Hz),5.33(1H,d,J=7.8Hz),5.46(1H,d,J=

        10.7Hz),5.56(1H,d,J=17.1Hz),5.90(1H,d,J=

        5.3Hz),6.16(1H,ddd,J=7.1Hz,J=10.7Hz,J=

        5.8Hz),7.47(2H,t,J=7.3Hz),7.59(1H,t,J=

        7.3Hz),8.11(2H,d,J=7.3Hz).参考例69β-10-脱乙?;?9-二氢-9,10-O-异亚丙基-7-O-三乙基甲硅烷基浆果赤霉素III

        用9β-10-脱乙?;?9-二氢-9,10-O-异亚丙基浆果赤霉素III作原料,重复参考例5步骤1的反应过程则得到标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.61(6H,q,J=7.8Hz),0.96(9H,t,J=7.8Hz),1.11

        ???(3H,s),1.40(3H,s),1.50(3H,s),1.57(3H,s),1.59

        ???(3H,s),1.93(3H,s),1.88-2.15(2H,m),2.23-2.47

        ???(2H,m),2.32(3H,s),3.16(1H,d,J=5.3Hz),4.17

        ???(1H,t,J=4.8Hz),4.17-4.29(1H,m),4.20(1H,d,

        ???J=7.8Hz),4.54(1H,d,J=7.8Hz),4.73-4.88(2H,

        ???m),5.51(1H,d,J=7.8Hz),5.91(1H,d,J=5.3Hz),

        ???7.48(2H,t,J=7.3Hz),7.59(1H,t,J=7.3Hz),8.14

        ???(2H,t,J=7.3Hz).参考例7步骤1:9β-10-脱乙?;?9-二氢-9,10-O-(2-亚丙烯基)-7,13-双-O-三乙基甲硅烷基浆果赤霉素III

        将2.115g参考例5步骤1所得化合物溶于150ml二氯甲烷中,于室温将该溶液与0.528ml?2,6-卢剔啶混合再冷至-58℃,随后滴加0.88ml三氟甲磺酸三乙基甲硅烷基酯。40分钟后,于-52℃再向该溶液加入0.176ml?2,6-卢剔啶和0.293ml三氟甲磺酸三乙基甲硅烷基酯。于-52℃将所得溶液与甲醇和饱和碳酸氢钠水溶液混合并用氯仿萃取,用饱和盐水洗涤该萃取液并经无水硫酸钠干燥。之后,在减压下蒸发溶剂并用硅胶柱色谱法(展开溶剂:己烷∶乙酸乙酯=6∶1(v/v))纯化所得残余物,则得到呈白色泡沫状的1.7763g标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.55-0.73(6H,m),0.99(9H,t,J?=7.8Hz),1.01(9H,

        ???t,J=7.8Hz),1.14(3H,s),1.52(3H,s),1.53(3H,

        ???s),1.72(1H,s),1.87(3H,s),2.01-2.16(2H,m),

        ???2.26(3H,s),3.21(1H,d,J=5.9Hz),3.92(1H,dd,

        ???J=10.7Hz,J=5.3Hz),4.32(1H,d,J=8.3Hz),4.39

        ???(1H,d,J=8.3Hz),4.59(1H,d,J=9.3Hz),4.83(1H,

        ???dd,J=8.7Hz,J=5.3Hz),4.94(1H,t,J=7.3Hz),

        ???5.05(1H,d,J=5.9Hz),5.30(1H,d,J=9.3Hz),5.44

        ???(1H,d,J=10.7Hz),5.82(1H,d,J=5.9Hz),6.12(1H,

        ???ddd,J=17.6Hz,J=10.7Hz,J=5.9Hz),7.46(2H,t,J

        ???=7.3Hz),7.57(1H,t,J=7.3Hz),8.08(2H,d,J=

        ???7.3Hz).步骤2:9β-4-O-丁?;?4,10-二脱乙?;?9-二氢-9,10-O-(2-亚丙烯基)-7,13-双-O-三乙基甲硅烷基浆果赤霉素III

        于0℃下将0.7671g上述步骤1所得化合物溶于37ml无水四氢呋喃中,再向其中滴加4.7ml双三甲基甲硅烷基氨基钠(1.0mol/L四氢呋喃溶液)。在滴加15分钟后,在相同温度下将该溶液与0.37ml乙基碘混合并搅拌30分钟。于0℃将所得溶液与饱和碳酸氢钠水溶液混合,用乙酸乙酯稀释以进行相分离,然后用乙酸乙酯萃取。用饱和盐水洗涤该萃取液,经无水硫酸钠干燥并在减压下浓缩,用硅胶柱色谱法纯化所得残余物(展开溶剂:己烷∶乙酸乙酯=7∶1(v/v))则得到0.2604g呈白色玻璃状的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.58-0.73(12H,m),0.93-1.10(21H,m),1.15(3H,

        ???s),1.52(3H,s),1.53(3H,s),1.70(1H,s),1.74-

        ???1.90(2H,m),1.85(3H,s),2.01-2.12(2H,m),2.17-

        ???2.30(1H,m),2.32-2.43(1H,m),2.45-2.63(2H,m),

        ???3.19(1H,d,J=5.9Hz),3.93(1H,dd,J=11.3Hz,J=

        ???5.4Hz),4.32(1H,d,J=8.3Hz),4.39(1H,d,J=

        ???8.3Hz),4.58(1H,d,J=8.8Hz),4.79(1H,dd,J=

        ???8.8Hz,J=4.9Hz),4.94(1H,t,J=8.3Hz),5.05(1H,

        ???d,J=5.9Hz),5.29(1H,d,J=8.8Hz),5.44(1H,d,

        ???J=10.8Hz),5.55(1H,d,J=17.6Hz),5.81(1H,d,J=

        ???5.9Hz),6.11(1H,ddd,J=17.6Hz,J=10.8Hz,J=

        ???5.9Hz),7.46(2H,t,J=7.8Hz),7.58(1H,t,J=

        ???7.8Hz),8.09(2H,d,J=7.8Hz).步骤3:9β-4-O-丁?;?4,10-二脱乙?;?9-二氢-9,10-O-(2-亚丙烯基)浆果赤霉素III

        于0℃将0.1414g上述步骤2所得化合物溶于7.0ml吡啶中,再向其中逐滴加入1.41ml氟化氢-吡啶。在滴加完成后,将该溶液与0℃冷水混合,用乙酸乙酯稀释以进行相分离,然后用乙酸乙酯萃取。用饱和盐水洗涤所得萃取液并经无水硫酸钠干燥。之后在减压浓缩萃取液,并用硅胶柱色谱法(展开溶剂:氯仿∶丙酮=7∶1(v/v))纯化所得残余物,则得到呈白色玻璃状的69.7mg标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.06(3H,s),1.16(3H,s),1.62(3H,s),1.65(3H,s),

        ???1.73-1.86(2H,m),1.90-2.00(1H,m),1.93(3H,s),

        ???2.10-2.29(3H,m),2.34(1H,dd,J=15.6Hz,J=

        ???9.7Hz),2.60(2H,t,J=7.8Hz),3.05(1H,d,J=

        ???4.9Hz),3.88(1H,d,J=6.8Hz),4.06-4.18(1H,m),

        ???4.33(1H,d,J=8.4Hz),4.40(1H,dd,J=8.4Hz,J=

        ???1.5Hz),4.59(1H,d,J=8.3Hz),4.78(1H,br?q,J=

        ???7.4Hz),5.02(1H,s),5.22(1H,d,J=5.9Hz),5.30

        ???(1H,d,J=6.8Hz),5.44(1H,d,J=10.8Hz),5.56(1H,

        ???d,J=17.1Hz),5.95-6.13(2H,m),7.48(2H,t,J=

        ???7.8Hz),7.60(1H,t,J=7.8Hz),8.14(2H,d,J=

        ???7.8Hz).步骤4:9β-4-O-丁?;?4,10-二脱乙?;?9-二氢-9,10-O-(2-亚丙烯基)-7-O-三乙基甲硅烷基浆果赤霉素III

        用上述步骤3所得化合物作原料,重复参考例5步骤1的反应过程,则得到标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.64(6H,q?like,J=7.8Hz),0.98(9H,t,J=7.8Hz),

        ???1.05(3H,s),1.41(3H,s),1.56(3H,s),1.61(3H,s),

        ???1.71-1.84(2H,m),1.76(1H,s),1.94(3H,s),1.95-

        ???2.63(7H,m),3.18(1H,d,J=4.8Hz),3.96(1H,dd,J

        ???=8.3Hz,J=5.8Hz),4.32(1H,d,J=8.3Hz),4.37(1H,

        ???d,J=8.3Hz),4.58(1H,br?d,J=7.8Hz),4.70-4.81

        ???(2H,m),5.10(1H,d,J=5.9Hz),5.33(1H,d,J=

        ???8.4Hz),5.46(1H,d,J=10.2Hz),5.57(1H,d,J=

        ???17.6Hz),5.90(1H,d,J=4.8Hz),6.16(1H,ddd,J=

        ???17.6Hz,J=10.2Hz,J=5.9Hz),7.47(2H,t,J=

        ???7.8Hz),7.59(1H,t,J=7.8Hz),8.11(2H,d,J=

        ???7.8Hz).参考例8步骤1:9β-4,10-二脱乙?;?9-二氢-4-O-丙?;?9,10-O-(2-亚丙烯基)浆果赤霉素III

        使用参考例7步骤1所得化合物作原料,重复参考例7步骤2的反应过程,不同之处是用甲基碘代替乙基碘。之后,重复参考例7步骤3的反应过程,则得到呈白色玻璃状的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.16(3H,s),1.26(3H,t,J=7.4Hz),1.62(3H,s),

        ???1.65(3H,s),1.82(1H,br?s),1.93(3H,s),2.09-

        ???2.25(3H,m),2.33(1H,dd,J=14.0Hz,J=10.0Hz),

        ???2.66(2H,q,J=7.4Hz),3.05(1H,d,J=4.9Hz),3.89

        ???(1H,d,J=7.4Hz),4.06-4.16(1H,br),4.33(1H,d,

        ???J=8.8Hz),4.39(1H,d,J=8.8Hz),4.53-4.63(1H,

        ???br),4.72-4.84(1H,br),5.02(1H,s?like),5.22(1H,

        ???d,J=6.4Hz),5.30(1H,d,J=7.4Hz),5.45(1H,d,

        ???J=10.8Hz),5.56(1H,d,J=17.6Hz),5.96-6.10(2H,

        ???m),7.47(2H,t,J=7.4Hz),7.60(1H,t,J=7.4Hz),

        ???8.13(2H,d,J=7.4Hz).步骤2:9β-4,10-二脱乙?;?9-二氢-4-O-丙?;?9,10-O-(2-亚丙烯基)-7-O-三乙基甲硅烷基浆果赤霉素III

        用上述步骤1所得化合物作原料,重复参考例5的步骤1的反应过程,则得到呈白色玻璃状的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.58-0.71(6H,m),0.98(9H,t,J=7.8Hz),1.09(3H,

        ???s),1.25(3H,s),1.56(3H,s),1.60(3H,s),1.75(1H,

        ???s),1.94(3H,s),1.98-2.16(2H,m),2.23-2.44(2H,

        ???m),2.62(2H,q,J=7.3Hz),3.19(1H,d,J=5.4Hz),

        ???3.96(1H,dd,J=8.8Hz,J=5.8Hz),4.32(1H,d,J=

        ???8.3Hz),4.37(1H,d,J=8.3Hz),4.59(1H,d,J=

        ???8.7Hz),4.71-4.82(2H,m),5.09(1H,d,J=5.9Hz),

        ???5.33(1H,d,J=8.7Hz),5.46(1H,d,J=10.8Hz),5.56

        ???(1H,d,J=17.6Hz),5.90(1H,d,J=5.4Hz),6.16(1H,

        ???ddd,J=17.6Hz,J=10.8Hz,J=5.9Hz),7.46(2H,t,

        ???J=7.3Hz),7.58(1H,t,J=7.3Hz),8.12(2H,d,J=

        ???7.3Hz).参考例9步骤1:9β-10-脱乙?;?9-二氢-9,10-O-异亚丙基-7,13-双-O-三乙基甲硅烷基浆果赤霉素III

        使用参考例6步骤1所得化合物作原料,重复参考例7步骤1的反应过程,则得到标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.56-0.70(12H,m),0.90-1.04(18H,m),1.15(3H,

        ???s),1.31(3H,s),1.37(3H,s),1.45(3H,s),1.55(3H,

        ???s),1.87(3H,s),2.03-2.36(4H,m),2.27(3H,s),

        ???3.20(1H,d,J=5.8Hz),3.94(1H,dd,J=9.2Hz,J=

        ???3.6Hz),4.42(1H,d,J=8.0Hz),4.50(1H,d,J=

        ???8.0Hz),4.54(1H,d,J=9.2Hz),4.83(1H,t,J=

        ???7.3Hz),4.94(1H,dd,J=8.2Hz,J=7.8Hz),5.41(1H,

        ???d,J=9.2Hz),5.7(1H,d,J=5.8H),7.44-7.84(2H,

        ???m),7.56-7.59(1H,m),8.07-8.09(2H,m).步骤2:9β-4-O-丁?;?4,10-二脱乙?;?9-二氢-9,10-O-异亚丙基-7,13-双-O-三乙基甲硅烷基浆果赤霉素III

        用上述步骤1所得化合物作原料,重复参考例1步骤2的反应过程,则得到呈无色玻璃固体的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.58-0.70(12H,m),0.91-1.07(21H,m),1.16(3H,

        ???s),1.38(3H,s),1.46(3H,s),1.47(3H,s),1.56(3H,

        ???s),1.85(3H,s),2.04-2.28(6H,m),2.53(1H,dt,

        ???J=8.0Hz,J=6.0Hz),2.54(1H,dt,J=8.0Hz,J=

        ???6.0Hz),3.19(1H,d,J=5.9Hz),3.97(1H,dd,J=

        ???9.9Hz,J=3.9Hz),4.37(2H,ABq,J=7.8Hz),4.54(1H,

        ???d,J=9.3Hz),4.80(1H,t,J=7.3Hz),4.94(1H,t,

        ???J=7.8Hz),5.41(1H,d,J=9.3Hz),5.79(1H,d,J=

        ???5.9Hz),7.46(2H,t,J=7.8Hz),7.57(1H,t,J=

        ???7.8Hz),8.10(2H,d,J=7.8Hz).FAB质谱:843(MH+)。步骤3:9β-4-O-丁?;?4,10-二脱乙?;?9-二氢-9,10-O-异亚丙基浆果赤霉素III

        用上述步骤2所得化合物作原料,重复参考例7的反应过程则得到呈无色玻璃固体的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.07(3H,s),1.16(3H,s),1.42(3H,s),1.58(3H,s),

        ???1.63(3H,s),1.64(3H,s),1.84(3H,s),1.93(3H,s),

        ???1.97-2.40(4H,m),2.59(2H,dd,J=7.8Hz,J=

        ???7.3Hz),3.06(1H,d,J=4.9Hz),3.85(1H,d,J=

        ???7.3Hz),4.10(1H,s),4.37(2H,ABq,J=8.5Hz),4.67

        ???(1H,d,J=7.8Hz),4.79(1H,dd,J=8.5Hz,J=

        ???5.7Hz),5.02(1H,br),5.59(1H,d,J=7.3Hz),6.03

        ???(1H,d,J=4.9Hz),7.48(2H,t,J=7.8Hz),7.60(1H,

        ???t,J=7.3Hz),8.13(2H,d,J=7.3Hz).步骤4:9β-4-O-丁?;?4,10-二脱乙?;?9-二氢-9,10-O-异亚丙基-7-O-三乙基甲硅烷基浆果赤霉素III

        用上述步骤3所得化合物作原料,重复参考例5步骤1的反应物过程则得到呈无色玻璃固体的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.61(6H,q,J=7.8Hz),0.95(9H,t,J=7.8Hz),1.06

        ???(3H,t,J=7.3Hz),1.13(3H,s),1.41(3H,s),1.51

        ???(3H,s),1.57(3H,s),1.59(3H,s),1.77-1.83(2H,

        ???m),1.94(3H,s),2.27-2.39(4H,m),2.59(2H,m),

        ???3.65(1H,d,J=5.4Hz),3.65(1H,dd,J=7.8Hz,J=

        ???4.4Hz),4.18(2H,ABq,J=7.8Hz),4.56(1H,d,J=

        ???7.8Hz),4.48-4.83(2H,m),5.52(1H,d,J=7.8Hz),

        ???5.93(1H,d,J=5.4Hz),7.43(2H,t,J=7.8Hz),7.59

        ???(1H,t,J=7.8Hz),8.15(2H,d,J=7.8Hz).参考例10步骤1:9β-4,10-二脱乙?;?9-二氢-9,10-O-异亚丙基-4-O-丙?;?7,13-双-O-三乙基甲硅烷基浆果赤霉素III

        在氮气氛下,于0℃将1.17ml二异丙胺溶于21ml无水四氢呋喃中,将该溶液与正丁基锂(1.69mol/l,己烷溶液)混合并搅拌20分钟。在冷至-78℃后,向其中滴加7ml含728mg参考例9步骤1所得化合物的无水四氢呋喃。1小时后,该溶液与-78℃的1.11ml甲基碘混合,搅拌4小时同时逐渐升温至-5℃。将所得溶液与饱和氯化铵水溶液混合并用乙酸乙酯萃取。用饱和盐水洗涤所得萃取液并经无水硫酸钠干燥。之后,在减压下蒸发溶剂并用硅胶柱色谱法(展开溶剂:己烷∶乙酸乙酯=10∶1(v/v))纯化所得残余物,则得到呈无色玻璃状固体的706mg标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.61-0.72(12H,m),0.91-1.02(18H,m),1.16(3H,

        ???s),1.25(3H,t,J=7.3Hz),1.38(3H,s),1.46(3H,

        ???s),1.50(3H,s),1.56(3H,s),1.85(3H,s),2.02-2.26

        ???(4H,m),2.63(2H,q,J=7.3Hz),3.19(1H,d,J=

        ???5.9Hz),3.96(1H,dd,J=9.3Hz,J=3.4Hz),4.30(2H,

        ???ABq,J=7.8Hz),4.54(1H,d,J=8.8Hz),4.80(1H,t,

        ???J=7.3Hz),4.95(1H,t,J=8.3Hz),5.40(1H,d,J=

        ???9.3Hz),5.78(1H,d,J=5.9Hz),7.46(2H,t,J=

        ???7.3Hz),7.58(1H,t,J=7.3Hz),8.10(2H,d,J=

        ???7.3Hz).FAB质谱:829(MH+)。步骤2:9β-4,10-二脱乙?;?9-二氢-9,10-O-异亚丙基-4-O-丙?;嗝顾豂II

        用上述步骤1所得化合物作原料,重复参考例7步骤3的反应过程则得到呈无色玻璃状固体的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.16(3H,s),1.27(3H,t,J=7.3Hz),1.42(3H,s),

        ???1.50(3H,s),1.63(3H,s),1.64(3H,s),1.94(3H,s),

        ???2.11-2.36(4H,m),2.66(2H,q,J=7.3Hz),3.06(1H,

        ???d,J=4.9Hz),3.85(1H,d,J=7.3Hz),4.52(2H,ABq,

        ???J=8.3Hz),4.67(1H,d,J=8.3Hz),4.79(1H,m),5.02

        ???(1H,s),5.59(1H,d,J=7.3Hz),6.02(1H,d,J=

        ???4.9Hz),7.47(2H,t,J=7.8Hz),7.60(1H,t,J=

        ???7.8Hz),8.14(2H,d,J=7.8Hz).步骤3:9β-4,10-二脱乙?;?9-二氢-9,10-O-异亚丙基-4-O-丙?;?7-O-三乙基甲硅烷基浆果赤霉素III

        用上述步骤2所得化合物作原料,重复参考例5步骤1的反应过程,则得到呈无色玻璃状固体的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.57-0.64(6H,m),0.93-0.98(9H,m),1.12(3H,s),

        ???1.26(3H,t,J=7.3Hz),1.40(3H,s),1.51(3H,s),

        ???1.57(3H,s),1.58(3H,s),1.77(1H,s),1.94(3H,s),

        ???1.96-2.35(4H,m),2.65(2H,q,J=7.3Hz),3.16(1H,

        ???d,J=5.6Hz),4.08(1H,t,J=4.9Hz),4.20(2H,d,

        ???J=7.8Hz),4.56(1H,d,J=7.8Hz),4.74-4.78(2H,

        ???m),5.20(1H,d,J=8.3Hz),5.93(1H,d,J=5.4Hz),

        ???7.46(2H,t,J=7.8Hz),7.59(1H,t,J=7.8Hz),8.15

        ???(2H,d,J=7.8Hz).FAB质谱:715(MH+)。参考例11步骤1:9β-10-脱乙?;?9-二氢-1-O-二甲基甲硅烷基-9,10-O-(2-亚丙烯基)-7,13-双-O-三乙基甲硅烷基浆果赤霉素III

        于室温下,将1.0789g参考例7步骤1所得化合物溶于26.9g?N,N-二甲基甲酰胺中,将该溶液与0.595g咪唑混合。向其中滴加0℃的0.736ml二甲基氯硅烷。搅拌1小时后,该溶液与0℃冷水混合,用己烷-乙酸乙酯混合溶剂(1∶1(v/v))萃取。用饱和盐水洗涤所得萃取液并经无水硫酸钠干燥。之后,在减压下蒸发溶剂并用硅胶柱色谱法(展开溶剂:己烷∶乙酸乙酯=9∶1(v/v))纯化所得残余物,则得到0.994g呈白色泡沫状的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???-0.34(3H,d,J=2.9Hz),0.03(3H,d,J=2.9Hz),0.58

        ???-0.76(12H,m),0.92-1.09(18H,m),1.11(3H,s),

        ???1.522(3H,s),1.528(3H,s),1.86(3H,s),2.02-2.16

        ???(1H,m),2.23-2.44(3H,m),2.26(3H,s),3.19(1H,

        ???d,J=5.3Hz),3.88(1H,dd,J=10.7Hz,J=4.9Hz),

        ???4.33(1H,d,J=7.8Hz),4.41(1H,d,J=7.8Hz),4.52

        ???-4.68(2H,m),4.83(1H,dd,J=8.8Hz,J=5.4Hz),

        ???4.98(1H,t,J=9.0Hz),5.04(1H,d,J=6.4Hz),5.27

        ???(1H,d,J=9.3Hz),5.42(1H,d,J=10.7Hz),5.53(1H,

        ???d,J=17.5Hz),5.89(1H,d,J=5.3Hz),6.11(1H,ddd,

        ???J=17.5Hz,J=10.7Hz,J=6.4Hz),7.45(2H,t,J=

        ???7.8Hz),7.56(1H,t,J=7.8Hz),8.10(2H,d,J=

        ???7.8Hz).步骤2:9β-4,10-二脱乙?;?9-二氢-1,O-二甲基甲硅烷基-9,10-O-(2-亚丙烯基)-7,13-双-O-三乙基甲硅烷基浆果赤霉素III

        将0.994g上述步骤1所得化合物溶于50ml无水四氢呋喃中,向其中滴加0℃的2.7ml双(2-甲氧基乙氧基)氢化铝钠(65%(w/v),甲苯溶液),在相同温度下搅拌5分钟。向其中加入0℃的250ml乙醚,然后逐渐加入70ml溶有12.8g酒石酸钾钠四水合物的水。加入完成后,将所得混合物升温至室温并剧烈搅拌1小时。用乙酸乙酯萃取所得溶液,用饱和盐水洗涤该萃取液并经无水硫酸钠干燥。之后,在减压下蒸发溶剂,并用硅胶柱色谱法(展开溶剂:己烷∶乙酸乙酯=9∶1(v/v))纯化所得残余物,则得到0.8413g呈无色玻璃状的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???-0.27(3H,d,J=2.4Hz),-0.01(3H,d,J=2.4Hz),

        ???0.54-0.67(6H,m),0.69-0.85(6H,m),0.95(3H,t,

        ???J=7.8Hz),0.97(3H,s),1.05(9H,t,J=7.9Hz),1.44

        ???(3H,s),1.55(3H,s),1.81(3H,s),2.10(1H,ddd,J=

        ???13.6Hz,J=9.6Hz,J=4.2Hz),2.20(1H,ddd,J=

        ???13.6Hz,J=8.2Hz,J=6.0Hz),2,52(1H,dd,J=

        ???14.7Hz,J=9.8Hz),2.87(1H,d,J=3.4Hz),3.01(1H,

        ???dd,J=14.7Hz,J=1.4Hz),3.62(1H,dd,J=9.6Hz,

        ???J=6.0Hz),3.78(1H,s?like),4.28(1H,d,J=7.9Hz),

        ???4.38-4.50(2H,m),4.50-4.69(2H,m),5.07(1H,d,

        ???J=6.4Hz),5.33(1H,d,J=7.9Hz),5.44(1H,d,J=

        ???10.2Hz),5.55(1H,d,J=17.1Hz),5.97(1H,d,J=

        ???3.5Hz),6.20(1H,ddd,J=17.1Hz,J=10.2Hz,J=

        ???6.4Hz),7.43(2H,t,J=7.4Hz),7.53(1H,t,J=

        ???7.4Hz),8.15(2H,d,J=7.4Hz).步骤3:9β-4-O-环丙烷羰基-4,10-二脱乙?;?9-二氢-1-O-二甲基甲硅烷基-9,10-O-(2-亚丙烯基)-7,13-双-O-三乙基甲硅烷基浆果赤霉素III

        将0.8413g上述步骤2所得化合物溶于40ml无水四氢呋喃中,向其中滴加0℃的3.1ml?1.0mol/l双三甲基甲硅烷基氨基锂(四氢呋喃溶液),15分钟后再加入0.24ml环丙烷碳酰氯。45分钟后,将该溶液与0℃的饱和氯化铵水溶液混合并用乙酸乙酯萃取。用饱和盐水洗涤所得萃取液并经无水硫酸钠干燥。之后减压下蒸发溶剂并用硅胶柱色谱法(展开溶剂:己烷∶乙酸乙酯=10∶1(v/v)→己烷∶乙酸乙酯=6∶1(v/v))纯化所得残余物,则得到0.8104g呈无色玻璃状的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???-0.33(3H,d,J=2.4Hz),0.04(3H,d,J=2.4Hz),0.57

        ???-0.75(12H,m),0.97(9H,t,J=7.8Hz),1.02(9H,t,

        ???J=7.8Hz),1.13(3H,s),1.20-1.46(2H,m),1.52

        ???(3H,s),1.56(3H,s),1.64-1.76(1H,m),1.87(3H,

        ???s),2.02(1H,ddd,J=14.4Hz,J=10.4Hz,J=4.4Hz),

        ???2.22-2.41(3H,m),3.15(1H,d,J=5.4Hz),3.88(1H,

        ???dd,J=10.4Hz,J=5.4Hz),4.25(1H,d,J=8.3Hz),

        ???4.34(1H,d,J=8.3Hz),4.52-4.64(2H,m),4.72(1H,

        ???dd,J=8.8Hz,J=4.4Hz),4.97(1H,t,J=8.3Hz),

        ???5.05(1H,d,J=5.7Hz),5.28(1H,d,J=8.8Hz),5.42

        ???(1H,d,J=10.3Hz),5.53(1H,d,J=17.6Hz),5.91

        ???(1H,d,J=5.4Hz),6.13(1H,ddd,J=17.6Hz,J=

        ???10.3Hz,J=5.7Hz),7.45(2H,t,J=7.4Hz),7.56(1H,

        ???t,J=7.4Hz),8.08(2H,d,J=7.4Hz).步骤4:9β-4-O-环丙烷羰基-4,10-二脱乙?;?9-二氢-9,10-O-(2-亚丙烯基)浆果赤霉素III

        用上述步骤3所得化合物作原料,重复参考例7步骤3的反应过程,则得到呈无色玻璃状标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.05-1.40(4H,m),1.17(3H,s),1.61(H,s),1.73-

        ???2.48(m),1.92(3H,s),3.04(1H,d,J=4.4Hz),3.86

        ???(1H,d,J=6.9Hz),4.03-4.18(1H,m),4.36(1H,d,J

        ???=8.3Hz),4.42(1H,d,J=8.3Hz),4.57(1H,d,J=

        ???8.3Hz),4.68-4.82(1H,m),4.98(1H,s?like),5.22

        ???(1H,d,J=5.9Hz),5.29(1H,d,J=6.9Hz),5.45(1H,

        ???d,J=10.2Hz),5.56(1H,d,J=17.1Hz),5.94-6.11

        ???(2H,m),7.48(2H,t,J=7.8Hz),7.60(1H,t,J=

        ???7.8Hz),8.13(2H,d,J=7.8Hz).步骤5:9β-4-O-环丙烷羰基-4,10-二脱乙?;?9-二氢-9,10-O-(2-亚丙烯基)-7-O-三乙基甲硅烷基浆果赤霉素III

        用上述步骤4所得化合物作原料,重复参考例5步骤1的反应过程,则得到呈无色玻璃状的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.58-0.72(6H,m),0.97(9H,t,J=7.8Hz),1.06-

        ???1.39(4H,m),1.10(3H,s),1.56(3H,s),1.62(3H,s),

        ???1.74-1.88(2H,m),1.98(3H,s),1.98-2.21(3H,m),

        ???2.28-2.44(2H,m),3.16(1H,d,J=5.3Hz),3.95(1H,

        ???dd,J=8.3Hz,J=5.9Hz),4.30(1H,d,J=8.3Hz),

        ???4.38(1H,d,J=8.3Hz),4.54(1H,d,J=7.8Hz),4.68

        ???-4.82(2H,m),5.10(1H,d,J=5.8Hz),5.33(1H,d,

        ???J=7.8Hz),5.45(1H,d,J=10.3Hz),5.56(1H,d,J=

        ???17.6Hz),5.93(1H,d,J=5.3Hz),6.16(1H,ddd,J=

        ???17.6Hz,J=10.3Hz,J=5.8Hz),7.47(2H,t,J=

        ???7.8Hz),7.60(1H,t,J=7.8Hz),8.11(2H,d,J=

        ???7.8Hz).参考例12步骤1:9β-10-脱乙?;?9-二氢-1-O-二甲基甲硅烷基-9,10-O-异亚丙基-7,13-双-O-三乙基甲硅烷基浆果赤霉素III

        用参考例8步骤1所得化合物作原料,重复参考例11步骤1的反应过程,则得到呈无色玻璃状的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???-0.33(3H,d,J=2.9Hz),0.04(3H,d,J=2.9Hz),0.58

        ???-0.72(12H,m),0.94-1.05(18H,m),1.12(3H,s),

        ???1.37(3H,s),1.47(3H,s),1.49(3H,s),1.57(3H,s),

        ???1.86(3H,s),2.09-2.36(4H,m),2.30(3H,s),3.19

        ???(1H,d,J=5.9Hz),3.91(1H,dd,J=8.8Hz,J=

        ???3.4Hz),4.40(2H,ABq,J=8.8Hz),4.50(1H,d,J=

        ???8.8Hz),4.57(1H,m),4.83(1H,t,J=7.3Hz),4.97

        ???(1H,t,J=8.3Hz),5.40(1H,d,J=8.8Hz),5.84(1H,

        ???d,J=5.4Hz),7.46(2H,t,J=7.8Hz),7.57(1H,t,

        ???J=7.8Hz),8.09(2H,d,J=7.8Hz).步骤2:9β-4,10-二脱乙?;?9-二氢-1-O-二甲基甲硅烷基-9,10-O-异亚丙基-7,13-双-O-三乙基甲硅烷基浆果赤霉素III

        用上述步骤1所得化合物作原料,重复参考例11步骤2的反应过程,则得到呈无色玻璃状标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???-0.27(3H,d,J=2.9Hz),0.01(3H,d,J=2.9Hz),0.58

        ???-0.83(12H,m),0.93-1.10(18H,m),1.08(3H,s),

        ???1.39(3H,s),1.46(3H,s),1.55?(3H,s),1.77(3H,s),

        ???1.84-2.40(4H,m),2.51(1H,dd,J=15.1Hz,J=

        ???10.0Hz),2.73(1H,d,J=5.9Hz),3.03(1H,dd,J=

        ???15.1Hz,J=2.4Hz),3.64(1H,s),3.86(1H,dd,J=

        ???7.3Hz,J=2.9Hz),4.05(1H,d,J=7.8Hz),4.09(1H,

        ???d,J=6,8Hz),4.43(1H,m),4.52(1H,d,J=6.8Hz),

        ???4.62-4.65(2H,m),5.54(1H,d,J=7.3Hz),5.57(1H,

        ???d,J=3.9Hz),7.44(2H,t,J=7.8Hz),7.55(1H,t,

        ???J=7.8Hz),8.19(2H,d,J=7.8Hz).步骤3:9β-4-O-环丙烷羰基-4,10-二脱乙?;?9-二氢-1-O-二甲基甲硅烷基-9,10-O-异亚丙基-7,13-双-O-三乙基甲硅烷基浆果赤霉素III

        用上述步骤2所得化合物作原料,重复参考例11步骤3的反应过程,则得到呈无色玻璃状标题化合物。??1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ?????-0.32(3H,d,J=2.4Hz),0.05(3H,d,J=2.4Hz),0.58

        ?????-0.71(12H,m),0.94-1.04(18H,m),1.16(3H,s),

        ?????1.21-1.36(4H,m),1.38(3H,s),1.48(3H,s),1.53

        ?????(3H,s),1.55(3H,s),1.71(1H,m),1.87(3H,s),2.05

        ?????-2.38(4H,m),3.13(1H,d,J=5.4Hz),3.87(1H,dd,

        ?????J=8.8Hz,J=3.4Hz),4.20(2H,ABq,J=7.8Hz),4.41

        ???(1H,d,J=8.8Hz),4.60(1H,m),4.43(1H,t,J=

        ???6.3Hz),4.99(1H,t,J=8.3Hz),5.42(1H,d,J=

        ???8.8Hz),5.88(1H,d,J=5.4Hz),7.46(2H,t,J=

        ???7.8Hz),7.57(1H,t,J=7.8Hz),8.10(2H,d,J=

        ???7.8Hz).FAB质谱:899(MH+)。步骤4:9β-4-O-环丙烷羰基-4,10-二脱乙?;?9-二氢-9,10-O-异亚丙基浆果赤霉素III

        用上述步骤3所得化合物作原料,重复参考例7步骤3的反应过程,则得到呈无色玻璃状的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.15-1.37(7H,m),1.41(3H,s),1.58(3H,s),1.64

        ???(6H,s),1.82-2.41(5H,m),1.73(3H,s),3.05(1H,

        ???d,J=4.9Hz),3.82(1H,d,J=6.8Hz),4.08(1H,br),

        ???4.39(2H,ABq,J=8.3Hz),4.67(1H,br),4.76(1H,t,

        ???J=7.2Hz),4.99(1H,s),5.59(1H,d,J=6.8Hz),6.06

        ???(1H,d,J=4.9Hz),7.48(2H,t,J=7.8Hz),7.60(1H,

        ???t,J=7.8Hz),8.13(2H,d,J=7.3Hz).FAB质谱:813(MH+)。步骤5:9β-4-O-环丙烷羰基-4,10-二脱乙?;?9-二氢-9,10-O-异亚丙基-7-O-三乙基甲硅烷基浆果赤霉素III

        用上述步骤4所得化合物作原料,重复参考例5的步骤1的反应过程,则得到呈无色玻璃状标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.58-0.64(6H,m),0.71-0.88(9H,m),1.05-1.22

        ???(4H,m),1.14(3H,s),1.41(3H,s),1.57(3H,s),1.60

        ???(3H,s),1.86-2.08(5H,m),1.93(3H,s),3.11(1H,

        ???d,J=4.9Hz),4.09-4.27(2H,m),4.50(2H,ABq,J=

        ???7.8Hz),4.71-4.80(2H,m),5.53(1H,d,J=7.8Hz),

        ???5.96(1H,d,J=4.8Hz),7.48(2H,t,J=7.8Hz),7.59

        ???(1H,t,J=7.8Hz),8.15(2H,d,J=7.3Hz).参考例13步骤1:9β-10-脱乙?;?7-脱氧-6,7-二脱氢-9-二氢-9,10-O-异亚丙基-13-O-三乙基甲硅烷基浆果赤霉素III

        于0℃将470mg参考例10步骤3所得化合物溶于45ml二氯甲烷中,将该溶液与15ml吡啶和570μl三氟甲磺酸酐混合。于室温搅拌1小时后,将该反应溶液倒入搅拌的由100ml乙醚和50ml饱和碳酸氢钠水溶液组成的混合物中,并用乙醚萃取。用饱和盐水洗涤所得萃取液并经无水硫酸钠干燥。之后,在减压下蒸发溶剂并用硅胶柱色谱法(展开溶剂:己烷∶乙酸乙酯=4∶1(v/v)→2∶1(v/v))纯化所得残余物,则得到240mg呈白色固体的标题化合物并回收到107mg原料。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.57-0.74(6H,m),1.01(9H,t,J=8.9Hz),1.20(3H,

        ???s),1.40(3H,s),1.51(3H,s),1.54(3H,s),1.57(3H,

        ???s),1.75(1H,s),1.84(3H,s),2.13(1H,dd,J=8.1,

        ???14.7Hz),2.22(1H,dd,J=8.6,14.7Hz),2.29(3H,s),

        ???3.09(1H,d,J=6.2Hz),4.14(1H,d,J=8.1Hz),4.27

        ???-4.33(2H,m),4.90(1H,d,J=4.3Hz),4.97(1H,br

        ???t,J=8.8Hz),5.48(1H,d,J=8.1Hz),5.66(1H,dd,J

        ???=10.3,4.3Hz),5.87(1H,d,J=6.2Hz),6.08(1H,d,J

        ???=10.3Hz),7.49(2H,t,J=7.8Hz),7.60(1H,t,J=

        ???7.8Hz),8.15(2H,d,J=7.8Hz).步骤2:9β-10-脱乙?;?7-脱氧-6,7-二脱氢-9-二氢-9,10-O-异亚丙基浆果赤霉素III

        用上述步骤1所得化合物作原料,重复本发明实施例1的步骤4的反应过程,则得到呈白色固体的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.13(3H,s),1.42(3H,s),1.53(3H,s),1.54(3H,s),

        ???1.59(3H,s),1.75(1H,s),1.91(3H,s),2.09(1H,dd,

        ???J=6.8,15.2Hz),2.20(1H,br?d,J=7.8Hz),2.34(1H,

        ???dd,J=8.8,15.2Hz),2.35(3H,s),3.22(1H,d,J=

        ???5.9Hz),4.04(1H,d,J=7.4Hz),4.26(1H,d,J=

        ???8.1Hz),4.34(1H,d,J=8.1Hz),4.72-4.87(1H,m),

        ???4.83(1H,d,J=4.4Hz),5.54(1H,d,J=7.4Hz),5.66

        ???(1H,dd,J=10.3,4.4Hz),5.93(1H,d,J=5.9Hz),

        ???6.12(1H,d,J=10.3Hz),7.48(2H,t,J=7.3Hz),7.60

        ???(1H,t,J=7.3Hz),8.18(2H,d,J=7.3Hz).参考例14步骤1:9β-10-脱乙?;?7-脱氧-9-二氢-7α-氟浆果赤霉素III

        于0℃下将26.1mg?10-脱乙?;?7-脱氧-7α-氟浆果赤霉素III溶于1.5ml四氢呋喃中,再将该溶液与1.5ml甲硼烷-四氢呋喃(1.0M四氢呋喃溶液)混合。在0℃搅拌6小时后,向其中滴加3.0ml甲醇,并在室温下搅拌该混合物30分钟。之后,在减压下蒸发溶剂并用硅胶薄层色谱法(展开溶剂:氯仿∶丙酮=3∶1(v/v))纯化该所得残余物,则得到呈无色透明玻璃状的30.8mg标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.14(3H,s),1.63(3H,s),1.71(3H,s),1.77(1H,s),

        ???1.87-1.90(3H,m),2.11(1H,dd,J=5.9,15.6Hz),

        ???2.15-2.52(4H,m),2.32(3H,s),3.34(1H,s),3.56

        ???(1H,d,J=4.9Hz),4.06(1H,d,J=5.4Hz),4.22(1H,

        ???d,J=8.3Hz),4.42(1H,d,J=8.3Hz),4.71(1H,dd,J

        ???=5.4,48.3Hz),4.72-4.83(1H,m),4.99(1H,d,J=

        ???7.8Hz),5.27(1H,br?s),6.08(1H,d,J=4.9Hz),7.48

        ???(2H,t,J=7.8Hz),7.59(1H,t,J=7.8Hz),8.11(2H,

        ???d,J=7.8Hz).步骤2:9β-10-脱乙?;?7-脱氧-9-二氢-7α-氟-9,10-O-异亚丙基浆果赤霉素III

        用上述步骤1所得化合物作原料,重复本发明实施例1步骤2的反应过程则得到呈无色透明玻璃状的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.12(3H,s),1.43(3H,s),1.49(3H,s),1.59(3H,s),

        ???1.65(3H,s),1.75(1H,s),1.98(3H,d,J=1.5Hz),

        ???2.00-2.45(5H,m),2.33(3H,s),3.59(1H,d,J=

        ???5.2Hz),4.30(1H,d,J=8.8Hz),4.35(1H,d,J=

        ???8.8Hz),4.61(1H,d,J=8.8Hz),4.75-4.85(1H,m),

        ???4.92(1H,ddd,J=3.4,10.3,45.9Hz),4.94(1H,d,J=

        ???3.9Hz),5.59(1H,d,J=8.8Hz),5.89(1H,d,J=

        ???5.2Hz),7.48(2H,t,J=7.4Hz),7.61(1H,t,J=

        ???7.4Hz),8.12(2H,d,J=7.4Hz).参考例15步骤1:10,13-双-O-苄氧基羰基-10-脱乙?;?7-O-三氟甲磺?;嗝顾豂II

        于0℃将470mg?10,13-二-O-苄氧基羰基-10-脱乙?;嗝顾豂II溶于20ml二氯甲烷中,再将该溶液与700mg?4-二甲氨基吡啶和480μl三氟甲磺酸酐混合。在0℃搅拌1小时后,将该反应溶液倒入由50ml乙酸乙酯和50ml冰水组成的混合物中并用乙酸乙酯萃取。用饱和碳酸氢钠水液洗涤所得萃取液并经无水硫酸钠干燥。之后在减压下蒸发溶剂并用硅胶柱色谱法(展开溶剂:氯仿∶乙酸乙酯=1∶1(v/v))纯化所得残余物,则得到370mg呈白色固体的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.10(3H,s),1.18(3H,s),1.68(1H,s),1.86(3H,s),

        ???2.13(3H,d,J=1.5Hz),2.18-2.45(3H,m),2.28(3H,

        ???s),2.78-2.93(1H,m),3.94(1H,d,J=6.8Hz),4.13

        ???(1H,d,J=8.3Hz),4.33(1H,d,J=8.3Hz),4.91(1H,

        ???d,J=8.3Hz),5.20(1H,d,J=12.2Hz),5.24(2H,s),

        ???5.25(1H,d,J=12.2Hz),5.50(1H,dd,J=7.3,

        ???10.3Hz),5.67(1H,d,J=6.8Hz),5.92(1H,t,J=

        ???8.1Hz),6.48(1H,s),7.27-7.39(10H,m),7.48(2H,

        ???t,J=7.3Hz),7.62(1H,t,J=7.3Hz),8.05(2H,d,

        ???J=7.3Hz).?步骤2:10,13-二-O-苄氧基羰基-10-脱乙?;?7-脱氧-7β,8β-亚甲基-19-降浆果赤霉素III

        将220mg上述步骤1所得化合物溶于12ml四氢呋喃和12ml乙腈中,将该溶液与6.0g硅胶混合并于60℃搅拌24小时。过滤去除硅胶后,将所得滤液与50ml乙酸乙酯和50ml饱和碳酸氢钠水溶液混合,并用乙酸乙酯萃取。用饱和盐水洗涤所得萃取液并经无水硫酸钠干燥。之后在减压下蒸发溶剂并用硅胶柱色谱法纯化所得残余物(展开溶剂:己烷∶乙酸乙酯=3∶1(v/v))则得到170mg呈白色固体的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.14(3H,s),1.22(3H,s),1.39(1H,br?s),1.58(1H,

        ???s),1.60-1.70(1H,m),1.94(3H,d,J=1.0Hz),2.09

        ???(1H,d,J=16.1Hz),2.23-2.40(3H,m),2.23(3H,s),

        ???2.45(1H,dt,J=16.1,4.4Hz),4.01(1H,d,J=

        ???7.3Hz),4.10(1H,d,J=8.8Hz),4.29(1H,d,J=

        ???8.8Hz),4.72(1H,d,J=3.9Hz),5.17-5.30(4H,m),

        ???5.63(1H,d,J=7.3Hz),5.80-5.92(1H,m),6.12(1H,

        ???s),7.28-7.50(10H,m),7.48(2H,t,J=7.3Hz),7.61

        ???(1H,t,J=7.3Hz),8.08(2H,d,J=7.3Hz).步骤3:10-脱乙?;?7-脱氧-7β,8β-亚甲基-19-降浆果赤霉素III

        将170mg上述步骤2所得化合物溶于10ml乙醇中,于室温将该溶液与34.0ml?10%钯-碳混合。在氢气氛下搅拌1小时后,过滤除去催化剂,在减压下蒸发所得滤液中的溶剂,然后用硅胶柱色谱法(展开溶剂:己烷∶乙酸乙酯=1∶1(v/v))纯化所得残余物,则得到110mg呈白色固体的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.11(3H,s),1.15(3H,s),1.35-1.43(1H,m),1.74

        ???(1H,dd,J=5.2,7.1Hz),1.76(1H,s),2.03(3H,d,J=

        ???1.0Hz),2.07-2.15(2H,m),2.27(3H,s),2.20-2.40

        ???(2H,m),2.45(1H,dt,J=15.6,4.4Hz),4.06(1H,d,J

        ???=7.8Hz),4.22(1H,d,J=1.0Hz),4.23(1H,d,J=

        ???8.3Hz),4.32(1H,d,J=8.3Hz),4.75(1H,d,J=

        ???3.9Hz),4.82-4.90(1H,m),5.04(1H,s),5.62(1H,d,

        ???J=7.8Hz),7.49(2H,t,J=7.3Hz),7.61(1H,t,J=

        ???7.3Hz),8.13(2H,d,J=7.3Hz).步骤4:9β-10-脱乙?;?7-脱氧-9-二氢-7β,8β-亚甲基-19-降浆果赤霉素III

        用上述步骤3所得化合物作原料,重复参考例14步骤1的反应过程,则得到呈无色透明玻璃状的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.92(1H,br?s),1.06-1.18(1H,m),1.14(3H,s),

        ???1.39-1.48(2H,m),1.67(3H,s),1.78(1H,s),1.83

        ???(3H,s),2.16(1H,d,J=4.9Hz),2.19(3H,s),2.34-

        ???2.40(1H,m),2.43(1H,dd,J=9.3,15.9Hz),2.53(1H,

        ???dd,J=7.1,15.9Hz),2.61(1H,d,J=7.8Hz),2.58-

        ???2.68(1H,m),3.25(1H,d,J=7.8Hz),3.87(1H,dd,

        ???J=5.4,7.8Hz),4.18(1H,d,J=7.3Hz),4.58(1H,dd,

        ???J=7.8,10.7Hz),4.69(1H,d,J=7.3Hz),4.70-4.80

        ???(1H,m),5.27(1H,dd,J=4.4,5.4Hz),5.55(1H,d,

        ???J=7.8Hz),7.47(2H,t,J=7.3Hz),7.58(1H,t,J=

        ???7.3Hz),8.04(2H,d,J=7.3Hz).步骤5:9β-10-脱乙?;?7-脱氧-9-二氢-7β,8β-亚甲基-9,10-O-异亚丙基-19-降浆果赤霉素III

        用上述步骤4所得化合物作原料,重复本发明实施例1步骤2的反应过程,则得到呈无色透明玻璃状的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.11(3H,s),1.20-1.40(2H,m),1.34(3H,s),1.48

        ???(3H,s),1,53(3H,s),1.68-1.80(2H,m),1.70(1H,

        ???s),1.76(1H,t,J=5.3Hz),1.92(3H,d,J=1.0Hz),

        ???2.09(1H,d,J=5.4Hz),2.22(3H,s),2.37(1H,dd,J

        ???=8.3,15.6Hz),2.47(1H,dd,J=7.3,15.6Hz),2.70

        ???(1H,dt,J=14.7,8.3Hz),3.31(1H,d,J=8.3Hz),

        ???4.22(1H,d,J=7.8Hz),4.40(1H,d,J=7.8Hz),4.49

        ???(1H,d,J=7.8Hz),4.57(1H,dd,J=8.2,9.2Hz),4.75

        ???-4.85(1H,m),5.49(1H,d,J=7.8Hz),5.50(1H,d,J

        ???=8.3Hz),7.43(2H,t,J=7.3Hz),7.59(1H,t,J=

        ???7.3Hz),8.05(2H,d,J=7.3Hz).参考例16步骤1:10-脱乙?;?10-O-甲?;嗝顾豂II

        将104mg?10-脱乙?;嗝顾豂II溶于1.0ml?N,N-二甲基甲酰胺中,将该溶液与0℃的70.7ml?4-二甲基氨基吡啶和96.0μl无水三氟甲磺酸混合。在0℃搅拌10分钟后,在搅拌下将该反应混合物与10ml乙酸乙酯和40ml水混合,然后用乙酸乙酯萃取。用饱和盐水洗涤该萃取液并经无水硫酸钠干燥。之后在减压下蒸发溶剂并用硅胶薄层色谱法(展开溶剂:氯仿∶乙酸乙酯=1∶2(v/v))纯化所得残余物,则得到94.3mg呈白色固体的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)??1.11(3H,s),1.12(3H,s),1.60(3H,s),1.69(3H.s),1.80-2.40(5H,m),??2.29(3H,s),2.53-2.62(1H,m),3.89(1H,d,J=6.8Hz),4.16(1H,d,J=8.7Hz).??4.31(1H,d,J=8.7Hz),4.40-4.50(1H,m),4.90(1H,br?q,J=5.6Hz),??4.98(1H,d,J=7.9Hz),5.64(1H,d,J=6.8Hz),6.46(1H,s),??7.50(2H,t,J=7.2Hz),7.61(1H,t,J=7.2Hz),8.10(2H,d,J=7.2Hz),??8.22(1H,s)步骤2:10-脱乙?;?10-O-甲?;?7-O-〔(1-咪唑基)-硫代羰基〕浆果赤霉素III

        将23.8mg上述步骤1所得化合物溶于0.50ml四氢呋喃中,于室温下将该溶液与0.50ml苯、12.5μl?1,8-二氮杂双环十一碳烯和12.5mg硫代羰基咪唑混合。在相同温度下搅拌1小时后,将该反应混合物与10ml乙酸乙酯和10ml饱和氯化铵水液混合,然后用乙酸乙酯萃取。用饱和盐水洗涤所得萃取液并经无水硫酸钠干燥。之后,在减压下蒸发溶剂并用硅胶薄层色谱法(展开溶剂:氯仿∶乙酸乙酯=1∶1(v/v))纯化所得残余物则得到21.4mg呈白色固体的标题化合物。??1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        1.13(3H,s),1.18(3H,s),1.64(3H,s),1.85-2.45(4H,m),1.96(3H,s),

        2.34(3H,s),2.49(1H,br?s),3.04(1H,ddd,J=7.1,J=9.3,J=14.3Hz),

        4.12(1H,d,J=7.3Hz),4.21(1H,d,J=8.6H2),4.38(1H,d,J=8.6Hz),

        4.88(1H,br?s),5.04(1H,d,J=9,3Hz),5.69(1H,d,J=7.3Hz),

        6.26(1H,dd,J=7.1,J=10.5Hz),6.40(1H,s),7.00(1H,s),

        7.50(2H,t,J=7.2H2),7.52(1H,s),7.63(1H,t,J=7.2Hz),7.99(1H,s),

        8.12(2H,d,J=7.2Hz),8.18(1H,s)步骤3:10-脱乙?;?7-脱氧-10-O-甲?;?7-O-浆果赤霉素III

        于室温下将140mg上述步骤2所得化合物溶于5.0ml二噁烷中,所得溶液与280μl三丁基氢化锡和10.0mg?2,2′-偶氮二异丁腈混合。在75-80℃温度搅拌40分钟后,将反应混合物与10ml乙酸乙酯、10ml水和10ml饱和盐水混合,然后用乙酸乙酯萃取。将所得萃取液经无水硫酸钠干燥。之后在减压下蒸发溶剂并用硅胶薄层色谱法(展开溶剂:己烷∶乙酸乙酯=5∶7(v/v))纯化所得残余物则得到52.0mg呈白色固体的标题化合物。??1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        1.09(3H,s),1.12(3H,s),1.50-2.50(8H,m),1.75(3H,s),2.04(3H,s),

        2.29(3H,s),3.85(1H,d,J=7.3Hz),4.19(1H,d,J=8.3Hz),

        4.32(1H,d,J=8.3Hz),4.85(1H,br?s),4.97(1H,dd,J=9.3,J=2.5Hz),

        5.63(1H,d,J=7.3Hz),6.60(1H,s),7.49(2H,t,J=7.3Hz),

        7.63(1H,t,J=7.3Hz),8.12(2H,d,J=7.3Hz),8.24(1H,s)步骤4:10-脱乙?;?7-脱氧浆果赤霉素III

        将50.0mg上述步骤3中所得的化合物溶于20ml的95%乙醇中,在室温下将该溶液与200μl水合肼混合。在室温下搅拌30分钟后,将该反应混合物与10ml乙酸乙酯和50ml?7%盐酸混合,然后用乙酸乙酯萃取。用饱和碳酸氢钠水液洗涤所得萃取液并经无水硫酸钠干燥。之后在减压下蒸发溶剂并用硅胶薄层色谱法(展开溶剂:己烷∶乙酸乙酯=2∶3(v/v))纯化所得残余物则得到30.0mg呈白色固体的标题化合物。?1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)???1.06(3H,s),1.09(3H,s),1.50-1.55(1H,m),1.80(1H,s),???1.90-2.41(7H,m),2.17(3H,s),2.29(3H,s),3.92(1H,d,J=7.3Hz),???4.17(1H,d,J=1.5Hz),4.22(1H,d,J=8.3Hz),4.33(1H,d,J=8.3Hz),???4.82-4.92(1H,m),4.96(1H,dd,J=9.6,J=3.2Hz),5.24(1H,d,J=1.5Hz),???5.62(1H,d,J=7.3Hz),7.48(2H,t,J=7.3Hz),7.61(1H,t,J=7.3Hz),???8.12(2H,d,J=7.3Hz)步骤5:9β-10-脱乙?;?7-脱氧-9-二氢浆果赤霉素III

        用上述步骤4所得化合物作原料,重复参考例14步骤1的反应过程,则得到呈无色透明玻璃状的标题化合物。??1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ?????1.15(3H,s),1.51(3H,s),1.67(3H,s),1.91(3H,s),

        ?????1.50-2.70(9H,m),2.35(3H,s),3.04(1H,d,J=

        ?????4.9Hz),3.14(1H,br?d,J=6.8Hz),3.75(1H,br?s),

        ?????4.21(1H,d,J=8.3Hz),4.37(1H,d,J=8.3Hz),4.71

        ?????(1H,br?q,J=8.3Hz),4.86(1H,br?s),5.45(1H,br

        ?????s),6.05(1H,d,J=4.9Hz),7.48(2H,t,J=7.6Hz),

        ?????7.61(1H,t,J.=7.6Hz),8.14(2H,d,J=7.6Hz).步骤6:9β-10-脱乙?;?7-脱氧-9-二氢-9,10-O-异亚丙基浆果赤霉素III

        用上述步骤5所得化合物作原料,重复本发明实施例1步骤2的反应过程则得到呈无色透明玻璃状的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.16(3H,s),1.43(3H,s),1.51(3H,s),1.57(3H,s),

        ???1.59(3H,s),1.79(1H,s),1.99(3H,s),1.45-2.40

        ???(6H,m),2.35(3H,s),2.44(1H,d,J=5.3Hz),3.10

        ???(1H,d,J=4.9Hz),4.19(1H,d,J=7.6Hz),4.27(1H,

        ???d,J=8.3Hz),4.34(1H,d,J=8.3Hz),4.70-4.84

        ???(1H,m),4.86(1H,br?s),5.62(1H,d,J=7.6Hz),5.97

        ???(1H,d,J=4.9Hz),7.48(2H,t,J=7.3Hz),7.60(1H,

        ???t,J=7.3Hz),8.14(2H,d,J=7.3Hz).参考例17步骤1:9β-10-脱乙?;?7-脱氧-9-二氢-9,10-O-(2-亚丙烯基)浆果赤霉素III

        将0.4800g参考例16步骤1所得化合物溶于9.6ml二氯甲烷中,于室温将该溶液与0.69ml丙烯醛缩二乙醇和19mg樟脑磺酸混合。20分钟后,将反应混合物冷至0℃并加入三乙胺将pH调至8。之后,在减压下浓缩反应溶液并用硅胶柱色谱法(展开溶剂:氯仿∶丙酮=12∶1(v/v))纯化所得残余物,则得到0.1823g呈白色玻璃固体的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.15(3H,s),1.48(3H,s),1.59(3H,s),1.72-2.22

        ???(4H,m),1.96(3H,s),2.22-2.40(1H,m),2.33(3H,

        ???s),2.55(1H,br?d,J=8.8Hz),3.06(1H,d,J=

        ???5.4Hz),4.19(1H,d,J=6.9Hz),4.23(1H,d,J=

        ???8.3Hz),4.32(1H,d,J=8.3Hz),4.77(1H,br),4.84

        ???(1H,s),5.23(1H,d,J=6.4Hz),5.32(1H,d,J=

        ???6.9Hz),5.44(1H,d,J=10.2Hz),5.57(1H,d,J=

        ???15.2Hz),5.92-6.13(2H,m),7.46(2H,t,J=7.8Hz),

        ???7.57(1H,t,J=7.8Hz),8.13(2H,d,J=7.8Hz).步骤2:9β-10-脱乙?;?7-脱氧-9-二氢-9,10-O-(2-亚丙烯基)-13-O-三乙基甲硅烷基浆果赤霉素III

        用上述步骤1所得化合物作原料,重复参考例7步骤1的反应过程,则得到呈白色玻璃状固体的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???0.58-0.76(6H,m),1.01(9H,s),1.25(3H,s),1.49

        ???(3H,s),1.61(3H,s),1.82-2.18(6H,m),1.93(3H,

        ???s),2.25(3H,s),2.92(1H,d,J=4.9Hz),4.14(1H,d,

        ???J=8.3Hz),4.24(1H,d,J=7.3Hz),4.34(1H,d,J=

        ???8.3Hz),4.93-5.05(2H,m),5.20(1H,d,J=6.4Hz),

        ???5.28(1H,d,J=7.3Hz),5.44.(1H,d,J=10.7Hz),5.56

        ???(1H,d,J=17.1Hz),5.91-6.09(2H,m),7.47(2H,t,

        ???J=7.8Hz),7.58(1H,t,J=7.8Hz),8.14(2H,d,J=

        ???7.8Hz).步骤3:9β-10-脱乙?;?7-脱氧-9-二氢-1-O-二甲基甲硅烷基-9,10-O-(2-亚丙烯基)-13-O-三乙基甲硅烷基浆果赤霉素III

        用上述步骤2所得化合物作原料,重复参考例11的步骤1的反应过程,则得到呈无色透明油状的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???-0.28(3H,d,J=2.9Hz),0.05(3H,d,J=2.9Hz),0.59

        ???-0.78(6H,m),1.02(9H,t,J=7.8Hz),1.19(3H,s),

        ???1.50-1.64(1H,m),1.53(3H,s),1.59(3H,s),1.82-

        ???2.04(3H,m),1.89(3H,s),2.14(1H,dd,J=15.1Hz,J=

        ???8.3Hz),2.26(3H,s),2.33(1H,dd,J=15.1Hz,J=

        ???8.8Hz),2.88(1H,d,J=4.8Hz),4.17(1H,d,J=

        ???8.3Hz),4.23(1H,d,J=7.3Hz),4.30(1H,d,J=

        ???8.3Hz),4.54-4.62(1H,m),4.94(1H,s),4.99(1H,t,

        ???J=8.3Hz),5.19(1H,d,J=6.3Hz),5.27(1H,d,J=

        ???7.3Hz),5.42(1H,d,J=10.7Hz),5.55(1H,d,J=

        ???17.1Hz),5.92-6.06(2H,m),7.45(2H,t,J=7.9Hz),

        ???7.56(1H,t,J=7.9Hz),8.14(2H,d,J=7.9Hz).步骤4:9β-4,10-二脱乙?;?7-脱氧-9-二氢-1-O-二甲基甲硅烷基-9,10-O-(2-亚丙烯基)-13-O-三乙基甲硅烷基浆果赤霉素III

        用上述步骤3所得化合物作原料,重复参考例11步骤2的反应过程,则得到呈浅黄色透明油状的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???-0.26(3H,d,J-2.9Hz),0.01(3H,d,J=2.9Hz),0.68

        ???-0.87(6H,m),1.03(3H,s),1.05(9H,t,J=7.8Hz),

        ???1.42(3H,s),1.52(3H,s),1.52-1.73(2H,m),1.80

        ???(3H,s),1.80-1.95(2H,m),2.52(1H,dd,J=15.1Hz,

        ???J=9.7Hz),2.71(1H,d,J=4.4Hz),2.85(1H,dd,J=

        ???15.1Hz,J=2.4Hz),3.61(1H,s),4.12-4.31(1H,m),

        ???4.14(1H,d,J=7.3Hz),4.18(1H,d,J=7.3Hz),4.25

        ???(1H,d,J=7.3Hz),4.57-4.70(3H,m),5.20(1H,d,J

        ???=6.3Hz),5.36(1H,d,J=7.3Hz),5.43(1H,d,J=

        ???10.3Hz),5.55(1H,d,J=17.1Hz),5.93-6.08(2H,m),

        ???7.44(2H,t,J=7.3Hz),7.54(1H,t,J=7.3Hz),8.17

        ???(2H,d,J=7.3Hz).步骤5:9β-4-O-环丙烷羰基-4,10-二脱乙?;?7-脱氧-9-二氢-1-O-二甲基甲硅烷基-9,10-O-(2-亚丙烯基)-13-O-三乙基甲硅烷基浆果赤霉素III

        用上述步骤4所得化合物作原料,重复参考例11步骤3的反应过程,则得到呈白色玻璃状的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???-0.28(3H,d,J=3.0Hz),0.05(3H,d,J=3.0Hz),0.56

        ???-0.80(6H,m),1.02(9H,t,J=7.8Hz),1.03-1.40

        ???(4H,m),1.21(3H,s),1.50-2.10(5H,m),1.51(3H,

        ???s),1.60(3H,s),1.90(3H,s),2.30(2H,d,J=

        ???8.8Hz),2.83(1H,d,J=4.9Hz),4.16(1H,d,J=

        ???8.3Hz),4.22(1H,d,J=7.4Hz),4.32(1H,d,J=

        ???8.3Hz),4.60-4.72(1H,m),4.89(1H,s),5.01(1H,t,

        ???J=8.3Hz),5.20(1H,d,J=8.3Hz),5.26(1H,d,J=

        ???7.4Hz),5.43(1H,d,J=10.3Hz),5.55(1H,d,J=

        ???17.6Hz),5.92-6.06(2H,m),7.45(2H,t,J-7.9Hz),

        ???7.57(1H,t,J=7.9Hz),8.11(2H,d,J=7.9Hz).步骤6:9β-4-O-环丙烷羰基-4,10-二脱乙?;?7-脱氧-9-二氢-9,10-O-(2-亚丙烯基)浆果赤霉素III

        用上述步骤5所得化合物作原料,重复参考例7步骤3的反应过程,则得到呈白色玻璃状的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.08-1.24(3H,m),1.17(3H,s),1.34-1.41(1H,m),

        ???1.47(3H,s),1.60(3H,s),1.60-1.94(5H,m),1.97

        ???(3H,s),2.04-2.12(1H,m),2.37(1H,d,J=9.8Hz),

        ???2.40(1H,d,J=11.7Hz),3.07(1H,d,J=5.4Hz),4.18

        ???(1H,d,J=6.8Hz),4.27(1H,d,J=8.7Hz),4.36(1H,

        ???d,J=8.7Hz),4.69-4.82(2H,m),5.23(1H,d,J=

        ???6.3Hz),5.33(1H,d,J=10.2Hz),5.57(1H,d,J=

        ???17.1Hz),5,96-6.08(2H,m),7.48(2H,t,J=7.3Hz),

        ???7.60(1H,t?like,J=7.3Hz),8.15(2H,d?like,J=

        ???7.3Hz).参考例18步骤1:9β-4,10-二脱乙?;?7-脱氧-9-二氢-1-O-二甲基甲硅烷基-4-O-乙氧基羰基-9,10-O-(2-亚丙烯基)-13-O-三乙基甲硅烷基浆果赤霉素III

        用参考例17步骤4所得化合物作原料,重复参考例11步骤3的反应过程,不同之处是用氯甲酸乙酯代替环丙烷碳酰氯,则得到呈无色透明油状的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???-0.28(3H,d,J=2.9Hz),0.03(3H,d,J=2.9Hz),0.56

        ???-0.75(6H,m),1.00(9H,t,J=7.8Hz),1.22(3H,s),

        ???1.39(3H,t,J=7.3Hz),1.50-1.70(2H,m),1.52(3H,

        ???s),1.60(3H,s),1.75-2.10(2H,m),1.89(3H,s),

        ???2.20-2.37(2H,m),2.80(1H,d,J=4.4Hz),4.15-

        ???4.26(3H,m),4.36-4.44(2H,m),4.60-4.68(1H,m),

        ???4.98-5.04(2H,m),5.20(1H,d,J=6.3Hz),5.26(1H,

        ???d,J=7.3Hz),5.43(1H,d,J=10.3Hz),5.55(1H,d,

        ???J=17.1Hz),5.91-6.07(2H,m),7.45(2H,t,J=

        ???7.8Hz),7.55(1H,t,J=7.8Hz),8.13(2H,d,J=

        ???7.8Hz).步骤2:9β-4,10-二脱乙?;?7-脱氧-9-二氢-4-O-乙氧基羰基-9,10-O-(2-亚丙烯基)浆果赤霉素III

        用上述步骤1所得化合物作原料,重复参考例7步骤3的反应过程,则得到白色玻璃状的标题化合物。1H-NMR(400?MHz,CDCl3/TMS)δ(ppm)

        ???1.16(3H,s),1.43(3H,t,J=7.3Hz),1.48(3H,s),

        ???1.54-2.15(5H,m),1.60(3H,s),1.97(3H,s),2.37

        ???(1H,dd,J=15.7Hz,J=9.8Hz),2.50(1H,d,J=

        ???10.3Hz),3.00(1H,d,J=4.9Hz),4.10-4.40(5H,m),

        ???4.65-4.80(1H,m),4.89(1H,s),5.23(1H,d,J=

        ???6.3Hz),5.34(1H,d,J=6.9Hz),5.46(1H,d,J=

        ???10.2Hz),5.57(1H,d,J=17.1Hz),5.92-6.08(2H,m),

        ???7.47(2H,t,J=7.8Hz),7.58(1H,t,J=7.8Hz),8.14

        ???(2H,d,J=7.8Hz).工业应用

        由下述试验实施例表明本发明化合物的抗肿瘤作用。试验实施例

        将三种肿瘤细胞系P388、PC-6和PC-12的每种细胞都接种于96井微量培养板中,接种物的量为5.0×102个细胞/150μl/每井(P388)、5.0×103个细胞/150μl/每井(P-6)、或1.0×103个细胞/150μl/每井(PC-12),对于P388是在2小时之后而对于另两种则在24小时之后,将每种50μl/井的样品加到该培养板上。之后,将这些细胞培养3天,然后将5mg/ml的MTT〔3-(4,5-二甲噻唑-2-基)-2,5-二苯基-2H-四唑溴化物〕溶液以20μl/井的量分配至该微量培养板的井内。四小时后,去除培养基,向每个井中加入150μl二甲亚砜,并测量于540nm的吸收度??怪琢鲂Ч山扛龈┳榈南赴鲋呈档椭炼哉兆榈?0%的每个药品的GI50值(ng/ml)来表示。结果示于下表中。

        ??????????????P388??????PC-6??????PC-12紫杉酚????????????4.36??????1.20??????82.2Taxotere??????????1.62??????1.16??????19.1本发明实施例22????0.0193????0.187?????0.181本发明实施例25????0.0549????1.31??????0.234本发明实施例51????0.00754???0.354?????0.0669本发明实施例53????0.0128????0.874?????0.0758本发明实施例57????0.0135????0.734?????0.0739本发明实施例60????0.0129????0.395?????0.0698本发明实施例65????0.00509???0.278?????0.0684本发明实施例69????0.0161????0.0915????0.0466本发明实施例70????0.00137???0.160?????0.0184本发明实施例79????0.00689???0.0673????0.0264本发明实施例8?????0.0048????0.0604????0.050本发明实施例90????0.0519????0.209?????0.0943本发明实施例95????0.0034????0.0992????0.0121本发明实施例98????0.0126????0.0696????0.022本发明实施例101???0.0301????0.409?????0.125本发明实施例105???0.0475????0.190?????0.0643本发明实施例121???0.00173???0.803?????0.0498本发明实施例123???0.0158????0.366?????0.167

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