ent-3α-Acetoxy-11α-bromo-10β-hydroxy-16-oxo-17,20-dinor-9α,15α-cyclogibberell-1-ene-7,19-dioic acid 7-(methyl ester) 19,10-lactone | 122054-23-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: ent-3α-Acetoxy-11α-bromo-10β-hydroxy-16-oxo-17,20-dinor-9α,15α-cyclogibberell-1-ene-7,19-dioic acid 7-(methyl ester) 19,10-lactone
• 英文别名: methyl (1S,2R,3S,5S,8S,9S,10R,11S,12S)-12-acetyloxy-3-bromo-11-methyl-6,16-dioxo-15-oxahexacyclo[9.3.2.15,8.01,10.02,7.02,8]heptadec-13-ene-9-carboxylate
• CAS: 122054-23-3
• 化学式: C₂₁H₂₁BrO₇
• 分子量: 465.298
• InChiKey: HWHDRKSMUJESRW-VVBWEORYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  29
• 可旋转键数：
  4
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  96
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  ent-3α-Acetoxy-11α-bromo-10β-hydroxy-16-oxo-17,20-dinor-9α,15α-cyclogibberell-1-ene-7,19-dioic acid 7-(methyl ester) 19,10-lactone 在 aluminum oxide 、 铑 4-二甲氨基吡啶 、 18-冠醚-6 、 dimethyl sulfide borane 、 氢气 、 双氧水 、 sodium acetate 、 四氯化钛 、 potassium carbonate 、 potassium hydrogencarbonate 、 三乙胺 、 N,N-二异丙基乙胺 、 锌 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 乙酸乙酯 、 苯 为溶剂， 反应 320.0h， 生成 ent-10β-hydroxy-3α,12α-bis(methoxymethoxy)-17-oxo-20-nor-17-epi-9α,15α-cyclogibberellane-7,19-dioic acid 7-(methyl ester) 19,10-lactone
  参考文献：
  名称：

  Synthesis of 3,12-dihydroxy 9,15-cyclogibberellins

  摘要：

  The methyl esters of 3,11- and 3,12-dihydroxy-9,15-cyclogibberellins have been synthesised from the gibberellin GA(7) with a view to determining the structure of a gibberellin-like antheridiogen isolated from prothallia of the fern Anemia phyllitidis, Introduction of an 11 alpha-hydroxyl was effected via S(N)2 substitution of an 11 beta-bromo-9,15-cyclogibberellin while hydroboration of an 11,16-diene provided access to the 3,12-dihydroxy isomers, Structures of the latter compounds were confirmed by X-ray crystallography. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(98)00843-6
• 作为产物：
  描述：

  Δ¹⁶-ent-3α-acetoxy-10β-hydroxy-20-norgibberell-1-en-7,19-dioic acid 19:10β-lactone 7-methyl ester 在 N-溴代丁二酰亚胺(NBS) 、 二甲基溴化硼 、 potassium hydride 、 臭氧 、 溶剂黄146 、 zinc dibromide 、 锌 、 过氧化苯甲酰 作用下， 以 四氢呋喃 、 四氯化碳 、 乙醚 、 二氯甲烷 为溶剂， 反应 6.0h， 生成 ent-3α-Acetoxy-11α-bromo-10β-hydroxy-16-oxo-17,20-dinor-9α,15α-cyclogibberell-1-ene-7,19-dioic acid 7-(methyl ester) 19,10-lactone
  参考文献：
  名称：

  New synthetic pathways from gibberellins to antheridiogens isolated from the fern genus Anemia

  摘要：

  DOI：

  10.1021/jo00303a020

文献信息

• Synthesis of New 9,15-Cyclogibberellins from Developing Apple Seeds: Confirmation of Structure for GA105 and GA108
  作者：Milan Pour、Petra Kraft-Klaunzer、Mark Furber、Lewis N. Mander、Bruce Twitchin、Naomi Oyama、Noboru Murofushi,、Hisakazu Yamane、Tadayuki Yamauchi

  DOI：10.1071/c96114

  日期：——

  The structures of two new gibberellins (GA105 and GA108) from developing apple seeds were confirmed as 2β- and 11β-hydroxy-9,15-cyclo-GA9, respectively, by synthesis of their methyl esters (7) and (8); the analogous 1α-, 2α- and 11α-isomers were also prepared, the last two being identified as metabolites of 9,15-cyclo-GA9 (2) formed in feeding experiments with fern prothallia of Lygodium circinnatum. The route to (7) began with the Birch reduction of gibberellic acid (GA3) methyl ester 3,13-dimesylate, thereby removing the oxygen substituents from C3 and C13. A series of iodolactonizations and elimination processes followed by ozonolysis of the 17-methylene group furnished (19) which, on treatment with potassium hydride, underwent intramolecular alkylation to afford the cyclogibberellin (20). Further functional group manipulation then led to (7) via its 2α-epimer (23). The previously prepared 11β-bromocyclogibberellin (28) was also subjected to a series of functional group manipulations and deletions to afford the 11α-hydroxy analogue (33), and thence the 11β-epimer (8) by means of an oxidation/reduction cycle; 1α-hydroxycyclo-GA9 methyl ester (26) was similarly prepared from the methyl ester of the known 1β-epimer (3).

  从发育中的苹果种子中提取的两种新赤霉素（GA105 和 GA108 GA105 和 GA108）的结构被证实为 2β-和 11β-羟基-9,15-环-GA9、 通过合成它们的甲酯 (7) 和 (8)，分别确认它们是 2β- 和 11β- 羟基-9,15-环-GA9；类似的 1α-、2α- 和 11α- 异构体也被制备出来，最后两种 被确定为 9,15-环-GA9（2）的代谢物。 的蕨类原叶喂食实验中形成的代谢物。 Lygodium circinnatum。获得 (7) 的途径始于 桦木还原赤霉素（GA3）甲酯 3,13-二甲酸酯，从而去除 C3 和 C13 中的氧取代基。A 一系列碘内酯化和消除过程，然后通过臭氧分解 生成了 (19)。 氢化钾处理后，发生分子内烷基化反应，得到环赤霉素（20）。 (20).进一步的官能团操作后，(7)通过其 2α-epimer (23)。之前制备的 11β-溴环赤霉素 (28) 也进行了一系列的官能团操作和缺失 通过一系列的官能团操作和缺失，得到了 11α-hydroxy 类似物 (33)，然后又得到了 11β-epimer (8)； 1α-羟基环-GA9 甲酯（26） 同样，1α-羟基环-GA9 甲酯（26）也是由已知的 1β-epimer (3) 的甲酯制备而成。
• An improved synthesis of antheridic acid, the antheridium inducing factor from the fern anemia phyllitidis
  作者：Mark Furber、Lewis N. Mander

  DOI：10.1016/0040-4039(88)85156-6

  日期：1988.1

  Antheridic acid (2) has been prepared by an improved route from gibberellin A7 (1).

  从赤霉素A 7（1）通过改进的路线制备了花酸（2）。
• Kaurenoids and gibberellins, including the newly characterized gibberellin A88, in developing apple seeds
  作者：Peter Hedden、Gordon V. Hoad、Paul Gaskin、Mervyn J. Lewis、Julia R. Green、Mark Furber、Lewis N. Mander

  DOI：10.1016/s0031-9422(00)94973-2

  日期：1993.1

  The ethyl acetate-soluble acids from extracts of immature apple seeds (Malus domestica cvs Cox's Orange Pippin, Dabinett, Sunset and Tremlett's Bitter) were analysed by combined gas chromatography-mass spectrometry. The following previously characterized gibberellins were identified by comparison of their mass spectra and Kovats retention indices with those of standards: GA1, GA3, GA4, GA7, GA9, GA12

  通过组合气相色谱-质谱法分析来自未成熟苹果种子（Malusdomestica cvs Cox's Orange Pippin、Dabinett、Sunset 和 Tremlett's Bitter）提取物的乙酸乙酯可溶性酸。通过将其质谱和 Kovats 保留指数与标准品的质谱和 Kovats 保留指数进行比较，鉴定了以下已表征的赤霉素：GA1、GA3、GA4、GA7、GA9、GA12、GA15、GA17、GA19、GA20、GA25、GA34、GA35、GA44、 GA45、GA53、GA54、GA61、GA62、GA63、GA68、GA80、GA84 和 3-epiGA54。此外，还检测到了大量的贝壳杉醇和赤霉素类化合物。确定了其中一种赤霉素与 ent-3α,10β-dihydroxy-20-norgibberella-9(11​​),16-diene-7,19-dioic acid 19