3β-tert-butyldimethylsilyloxy-5α,6β-dihydroxypregnan-20-one

• 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-tert-butyldimethylsilyloxy-5α,6β-dihydroxypregnan-20-one
• 英文别名: 3β-tert-butyldimethylsililoxy-5α,6β-dihydroxypregnan-20-one；1-[(3S,5R,6R,8S,9S,10R,13S,14S,17S)-3-[tert-butyl(dimethyl)silyl]oxy-5,6-dihydroxy-10,13-dimethyl-1,2,3,4,6,7,8,9,11,12,14,15,16,17-tetradecahydrocyclopenta[a]phenanthren-17-yl]ethanone
• 化学式: C₂₇H₄₈O₄Si
• 分子量: 464.761
• InChiKey: GKKQYASVFCKQFR-BKTJXCOPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.71
• 重原子数：
  32
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.96
• 拓扑面积：
  66.8
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3β-tert-butyldimethylsilyloxy-5α,6β-dihydroxypregnan-20-one 在 碘 、 mercury(II) oxide 作用下， 以 四氯化碳 、 二氯甲烷 为溶剂， 反应 4.5h， 以65%的产率得到3β-tert-butyldimethylsilyloxy-19-formyloxy-7-iodo-6-nor-5,7-secopregnane-5,20-dione
  参考文献：
  名称：

  Synthesis of 6-thia analogs of the natural neurosteroid allopregnanolone

  摘要：

  A procedure is described for the preparation of 6-thiapregnanes in five steps from pregnenolone via a 5-oxo-7-iodo-secopregnane intermediate. The 6-thiasteroid obtained was converted into 6-thia-allopregnanolone and its sulfoxide and sulforic derivatives. The trans stereochemistry at the A/B ring junction was accomplished by stereoselective reduction of an intermediate hemithioketal with triethylsilane/BF3 center dot Et2O. The compounds synthesized are analogs of natural neurosteroids, and exhibited GABA(A) receptor activity comparable to allopregnanolone. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2006.03.025
• 作为产物：
  描述：

  孕烯醇酮 在 咪唑 、 甲酸 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 22.83h， 生成 3β-tert-butyldimethylsilyloxy-5α,6β-dihydroxypregnan-20-one
  参考文献：
  名称：

  Synthesis of 6-thia analogs of the natural neurosteroid allopregnanolone

  摘要：

  A procedure is described for the preparation of 6-thiapregnanes in five steps from pregnenolone via a 5-oxo-7-iodo-secopregnane intermediate. The 6-thiasteroid obtained was converted into 6-thia-allopregnanolone and its sulfoxide and sulforic derivatives. The trans stereochemistry at the A/B ring junction was accomplished by stereoselective reduction of an intermediate hemithioketal with triethylsilane/BF3 center dot Et2O. The compounds synthesized are analogs of natural neurosteroids, and exhibited GABA(A) receptor activity comparable to allopregnanolone. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2006.03.025

文献信息

• Oxidation of Olefins with Benzeneseleninic Anhydride in the Presence of TMSOTf
  作者：Izabella Jastrzębska、Maja Morawiak、Joanna E. Rode、Barbara Seroka、Leszek Siergiejczyk、Jacek W. Morzycki

  DOI：10.1021/acs.joc.5b00410

  日期：2015.6.19

  been shown that different products are formed with this species depending on the specific structure of olefin. The 1,1-disubstituted olefins afforded mostly α,β-unsaturated carbonyl compounds. The sterically encumbered tri- or tetrasubstituted olefins yielded 1,2- or 1,4-dihydroxylated products, presumably via four-membered cyclic intermediates.

  研究了一种新的烯烃氧化体系，该体系由苯硒酸酐和三甲基甲硅烷基三氟甲磺酸酯组成。推测在这些条件下形成了高反应性的苯硒烯基阳离子。已经表明，取决于烯烃的具体结构，与该物质形成不同的产物。1，1-二取代的烯烃主要提供α，β-不饱和羰基化合物。在空间上受阻的三或四取代的烯烃产生了1,2-或1,4-二羟基化的产物，大概是通过四元环状中间体。
• Synthesis of 6-thia analogs of the natural neurosteroid allopregnanolone
  作者：Fernando J. Durán、Alberto A. Ghini、Hector Coirini、Gerardo Burton

  DOI：10.1016/j.tet.2006.03.025

  日期：2006.5

  A procedure is described for the preparation of 6-thiapregnanes in five steps from pregnenolone via a 5-oxo-7-iodo-secopregnane intermediate. The 6-thiasteroid obtained was converted into 6-thia-allopregnanolone and its sulfoxide and sulforic derivatives. The trans stereochemistry at the A/B ring junction was accomplished by stereoselective reduction of an intermediate hemithioketal with triethylsilane/BF3 center dot Et2O. The compounds synthesized are analogs of natural neurosteroids, and exhibited GABA(A) receptor activity comparable to allopregnanolone. (c) 2006 Elsevier Ltd. All rights reserved.