3β,11α-dihydroxy-17a-oxa-D-homo-5α-androstan-17-one | 956413-09-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 类固醇和类固醇衍生物
• 英文名称: 3β,11α-dihydroxy-17a-oxa-D-homo-5α-androstan-17-one
• 英文别名: (4aS,4bR,6aS,8S,10aS,10bS,11R,12aS)-8,11-dihydroxy-10a,12a-dimethyl-3,4,4a,4b,5,6,6a,7,8,9,10,10b,11,12-tetradecahydronaphtho[2,1-f]chromen-2-one
• CAS: 956413-09-5
• 化学式: C₁₉H₃₀O₄
• 分子量: 322.445
• InChiKey: KINLJDMAUPWNHF-OAZQVCGISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  23
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  66.8
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  雄酮 在 Beauveria bassiana KCH 1065 作用下， 以 丙酮 为溶剂， 反应 120.0h， 生成 3β,11α-dihydroxy-17a-oxa-D-homo-5α-androstan-17-one
  参考文献：
  名称：

  Microbial Baeyer–Villiger oxidation of 5α-steroids using Beauveria bassiana. A stereochemical requirement for the 11α-hydroxylation and the lactonization pathway

  摘要：

  Beauveria bassiana KCH 1065, as was recently demonstrated, is unusual amongst fungal biocatalysts in that it converts C-19 3-oxo-4-ene and 3 beta-hydroxy-5-ene as well as 3 beta-hydroxy-5 alpha-saturated steroids to 11 alpha-hydroxy ring-D lactones. The Baeyer-Villiger monooxygenase (BVMO) of this strain is distinguished from other enzymes catalyzing BVO of steroidal ketones by the fact that it oxidizes solely substrates with 11 alpha-hydroxyl group. The current study using a series of 5 alpha-saturated steroids (androsterone, 3 alpha-androstanediol and androstanedione) has highlighted that a small change of the steroid structure can result in significant differences of the metabolic fate. It was found that the 3 alpha-stereochemistry of hydroxyl group restricted "normal" binding orientation of the substrate within 11 alpha-hydroxylase and, as a result, androsterone and 3 alpha-androstanediol were converted into a mixture of 7 beta-, 11 alpha- and 7 alpha-hydroxy derivatives. Hydroxylation of androstanedione occurred only at the 11 alpha-position, indicating that the 3-oxo group limits the alternative binding orientation of the substrate within the hydroxylase. Only androstanedione and 3 alpha-androstanediol were metabolized to hydroxylactones. The study uniquely demonstrated preference for oxidation of equatorial (11 alpha-, 7 beta-) hydroxyketones by BVMO from B. bassiana. The time course experiments suggested that the activity of 17 beta-HSD is a factor determining the amount of produced ring-D lactones. The obtained 11 alpha-hydroxylactones underwent further transformations (oxy-red reactions) at C-3. During conversion of androstanedione, a minor dehydrogenation pathway was observed with generation of 11 alpha,17 beta-dihydroxy-5 alpha-androst-1-en-3-one. The introduction of C1-C2 double bond has been recorded in B. bassiana for the first time. (C) 2014 Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.steroids.2014.01.006

文献信息

• Microbial Baeyer–Villiger oxidation of steroidal ketones using Beauveria bassiana: Presence of an 11α-hydroxyl group essential to generation of D-homo lactones
  作者：Alina Świzdor、Teresa Kołek、Anna Panek、Agata Białońska

  DOI：10.1016/j.bbalip.2011.01.005

  日期：2011.4

  a rare reduction to 11α-hydroxy-5β-dihydrotestosterone. The experiments have demonstrated that the Baeyer–Villiger monooxygenase produced by the strain catalyzes solely oxidation of C-20 or C-17 ketones with 11α-hydroxyl group. 17-Oxo steroids, beside the 11α-hydroxylation and Baeyer–Villiger oxidation, also underwent reduction to 17β-alcohols; activity of 17β-hydroxysteroid dehydrogenase (17β-HSD)

  本文首次证明了最常用的全细胞生物催化剂球孢白僵菌（Beauveria bassiana）将一系列17-氧代甾族底物（表雄酮，脱氢表雄酮，雄烯二酮）转化为11α-羟基-17a-氧杂d-均一-17种产物，按以下反应顺序进行：11α-羟基化和随后的Baeyer-Villiger氧化成环D内酯。孕酮代谢第一阶段的产物11α-羟基孕酮沿两种途径进一步转化：羟基化为6β，11α-二羟基孕酮或17β-乙酰基链降解，从而导致11α-羟基睾酮（底物的主要代谢产物）。11α-羟基睾丸激素的一部分罕见地还原为11α-羟基-5β-二氢睾丸激素。实验表明，该菌株产生的Baeyer-Villiger单加氧酶仅催化带有11α-羟基的C-20或C-17酮的氧化。除11α-羟基化和Baeyer-Villiger氧化外，17-氧代类固醇也被还原为17β-醇。17β羟基类固醇脱氢酶（17β-HSD）的活性对所形成的环-的量显著冲击d