16α,17α-epoxy-5α-androstane

• 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: 16α,17α-epoxy-5α-androstane
• 英文别名: 16α,17α-Epoxy-5α-androstan；(1R,2S,4R,6S,7S,10S,11S,16R)-7,11-dimethyl-5-oxapentacyclo[8.8.0.02,7.04,6.011,16]octadecane
• 化学式: C₁₉H₃₀O
• 分子量: 274.447
• InChiKey: SAQQLIWLXDUYOI-LBYBGDIDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  20
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  16α,17α-epoxy-5α-androstane 在 sodium azide 、 copper(ll) sulfate pentahydrate 、 溶剂黄146 、 sodium ascorbate 作用下， 以 二氯甲烷 、 水 、 二甲基亚砜 为溶剂， 反应 12.0h， 生成 16β-(4-(acetoxymethyl)-1H-1,2,3-triazol-1-yl)-17α-hydroxy-5α-androstane
  参考文献：
  名称：

  Synthesis of ferrocene-labeled steroids via copper-catalyzed azide–alkyne cycloaddition. Reactivity difference between 2β-, 6β- and 16β-azido-androstanes

  摘要：

  Copper-catalyzed cycloaddition of steroidal azides and ferrocenyl-alkynes were found to be an efficient methodology for the synthesis of ferrocene-labeled steroids. At the same time, a great difference between the reactivity of 2 beta- or 16 beta-azido-androstanes and a sterically hindered 6 beta-azido steroid toward both ferrocenyl-alkynes and simple alkynes, such as phenylacetylene, 1-octyne, propargyl acetate and methyl propiolate, was observed. (C) 2012 Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.steroids.2012.04.005
• 作为产物：
  描述：

  (5alpha)-雄甾烷-17-酮 在 甲醇 、 sodium tetrahydroborate 、 乙醚 、 氯仿 、 溴 、 溶剂黄146 、 锌 作用下， 生成 16α,17α-epoxy-5α-androstane
  参考文献：
  名称：

  Shoppee et al., Journal of the Chemical Society, 1958, p. 3048,3057

  摘要：

  DOI：

文献信息

• 798. Steroids. Part XLIII. Comparison of the 16-bromo-17-ketones and 16-bromo-17-alcohols in the 3-unsubstituted and 3β-oxygenated 5α-androstone series
  作者：J. Fajkoš

  DOI：10.1039/jr9590003966

  日期：——
• Selective ring-opening carbonylation of epoxy-steroids☆
  作者：Attila Balázs、Csilla Benedek、Gábor Szalontai、Szilárd Tőrös

  DOI：10.1016/j.steroids.2004.02.003

  日期：2004.4

  Ring-opening alkoxycarbonylation of epoxy-steroids has been carried out with a Co-2(CO)(8)/3-hydroxypyridine catalytic system. High chemo- and regioselectivities were obtained under the reaction conditions applied. Structural analysis of the products proved their high stereochemical purity in each case, accompanied by inversion of the original configuration. No carbonylation took place for sterically hindered steranic epoxides. (C) 2004 Elsevier Inc. All rights reserved.
• Ionic Liquid-Promoted Wagner–Meerwein Rearrangement of 16α,17α-Epoxyandrostanes and 16α,17α-Epoxyestranes
  作者：Anita Horváth、Ágota Szájli、Róbert Kiss、János Kóti、Sándor Mahó、Rita Skoda-Földes

  DOI：10.1021/jo2006285

  日期：2011.8.5

  Ionic liquids 1-butyl-3-methylimidazolium hexafluorophosphate ([bmitn](+)[PF(6)](-)) and 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim](-)(+)[BF(4)](-)) were found to promote an unusual Wagner-Meerwein rearrangement of steroidal 16 alpha,17 alpha-epolddes leading to unnatural 13-epi-18-nor-16-one derivatives as the main products. These compounds were isolated in good to excellent yields. 16 alpha-Hydroxy-Delta(13)-18-norsteroid5, the results of the usual rearrangement, were obtained as minor components of the reaction mixtures. The ionic liquid [bmim](+)[PF(6)](-) was shown to induce C-ring aromatization of 16 alpha,17 alpha-epoxyestranes due to the formation of HF, the hydrolysis product of [PF(6)](-). Increasing amounts of HF and [PO(2)F(2)](-) were detected by (19)F and (31)P NMR when the ionic liquid was reused. The structures of the steroidal products, 16-oxo-18-nor-13 alpha-steroid derivatives, 16 alpha-hydroxy-Delta(13)-18-norsteroids, and C-aromatic compounds were determined by two-dimensional NMR techniques and high-resolution mass spectrometry (HRMS). The ionic liquids were recirculated efficiently.