(22R,23R,24S)-6β-methoxy-24-methyl-3α,5-cyclo-5α-cholestane-22,23-diol | 86014-17-7

• 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: (22R,23R,24S)-6β-methoxy-24-methyl-3α,5-cyclo-5α-cholestane-22,23-diol
• 英文别名: (22R,23R,24S)-6β-methoxy-24-methyl-3α,5-cyclo-5α-cholestan-22,23-diol；(2S,3R,4R,5S)-2-[(1S,2R,5R,7R,8R,10S,11S,14R,15S)-8-methoxy-2,15-dimethyl-14-pentacyclo[8.7.0.02,7.05,7.011,15]heptadecanyl]-5,6-dimethylheptane-3,4-diol
• CAS: 86014-17-7
• 化学式: C₂₉H₅₀O₃
• 分子量: 446.714
• InChiKey: CIFAEKPTTFBWTR-OADTURDHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.4
• 重原子数：
  32
• 可旋转键数：
  6
• 环数：
  5.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  49.7
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (22R,23R,24S)-6β-methoxy-24-methyl-3α,5-cyclo-5α-cholestane-22,23-diol 在 水 、 对甲苯磺酸 作用下， 以 1,4-二氧六环 为溶剂， 反应 4.0h， 以99%的产率得到6-deoxoteasterone
  参考文献：
  名称：

  Takatsuto, Suguru; Watanabe, Tsuyoshi; Fujioka, Shozo, Journal of Chemical Research, Miniprint, 1997, # 4, p. 901 - 924

  摘要：

  DOI：
• 作为产物：
  描述：

  (22E)-6β-methoxy-3α,5-cyclo-24-α-methyl-5α-cholest-22-ene 在 potassium osmate 、 甲基磺酰胺 、 potassium carbonate 、 氢化奎尼定 1,4-(2,3-二氮杂萘)二醚 、 potassium hexacyanoferrate(III) 作用下， 以 水 、 叔丁醇 为溶剂， 反应 30.0h， 以70%的产率得到(22R,23R,24S)-6β-methoxy-24-methyl-3α,5-cyclo-5α-cholestane-22,23-diol
  参考文献：
  名称：

  Highly Stereocontrolled Formal Synthesis of Brassinolide via Chiral Sulfoxide-Directed S_N2‘ Reactions

  摘要：

  An efficient stereocontrolled methodology for the preparation of the four contiguous chiral centers of the brassinosteroid side chain is described. Allylic mesyloxy sulfinyl steroids have been found to undergo highly stereoselective S(N)2' displacements when treated with cyanocuprates that provide the required acyclic stereocontrol in the key C-24 position of the steroidal side chain. Preparation of a direct precursor of brassinolide]I, as well as a precursor of naturally occurring (24R)-epibrassinolide, (+)-18, is carried out in two additional steps utilizing asymmetric dihydroxylations of(22E)-olefins (+)-2 and (+)-17. In this manner, a formal synthesis of this plant growth promoter has been completed, and the extension of the scope of this methodology has been explored providing a straightforward route to this family of steroids. Alternative routes to the key olefin (+)-2 are also outlined. Improved selectivity in the addition to aldehyde 7 for the preparation of the Cram (22R)-allylic hydroxy sulfoxides is achieved by controlling the chirality at sulfur or by a condensation-symmetric oxidation sequence employing the analogous vinyl sulfide reagent 22.

  DOI：

  10.1021/jo951264k

文献信息

• A short convergent synthesis of the side chains of brassinolide, cathasterone, and cryptolide
  作者：Alaksiej Hurski、Vladimir Zhabinskii、Vladimir Khripach

  DOI：10.1016/j.tetlet.2012.11.094

  日期：2013.2

  22α-hydroxy-23-ketone moieties characteristic of brassinolide and its congeners, has been developed. The key step is the coupling of a steroidal C-22 aldehyde with an anion derived from a specially synthesized thioacetal-containing chiral synthon. The cathasterone and cryptolide side chains are prepared by reductive or hydrolytic thioketal removal, respectively. The brassinolide side chain is obtained by DIBAL-H

  已经开发出一种新的方法来制备喜树碱系列的甾族衍生物，其含有油菜素内酯及其同类物的22α-羟基-，22α，23α-二羟基-和22α-羟基-23-酮部分。关键步骤是将类固醇C-22醛与衍生自特殊合成的含硫缩醛的手性合成子的阴离子偶联。分别通过还原性或水解性硫代缩酮去除来制备Cathasterone和cryptolide侧链。通过DIBAL-H还原TBS保护的22α-羟基-23-酮获得油菜素内酯侧链。
• Khripach; Zhabinskii; Zhernosek, Russian Journal of Organic Chemistry, 1996, vol. 32, # 5, p. 662 - 667
  作者：Khripach、Zhabinskii、Zhernosek

  DOI：——

  日期：——
• ——
  作者：V. A. Khripach、V. N. Zhabinskii、N. D. Pavlovskii

  DOI：10.1023/a:1013804119279

  日期：——

  A biosynthetic precursor of brassinolide, (22R,23R,24S)-24-methyl-3alpha-cholestane-3beta,6alpha,22,23-tetraol was synthesized from Delta(23)-22-keto steroid which was obtained from the corresponding 20-carbonitrile oxide. The side chain was built up by a series of successive transformations: hydride reduction of the initial enone, epoxidation of the allyl-like alcohol, and copper(I) cyanide-catalyzed opening of the 23,24-epoxy ring. The cyclic fragment was completed by opening of the cyclopropane ring with subsequent hydroboration and oxidation of the Delta(5)-bond.
• NAKAI, TAKEHSI;MIKAMI, KOITI
  作者：NAKAI, TAKEHSI、MIKAMI, KOITI

  DOI：——

  日期：——
• Takatsuto, Suguru; Watanabe, Tsuyoshi; Fujioka, Shozo, Journal of Chemical Research, Miniprint, 1997, # 4, p. 901 - 924
  作者：Takatsuto, Suguru、Watanabe, Tsuyoshi、Fujioka, Shozo、Sakurai, Akira

  DOI：——

  日期：——