5α-cholestane-3α,3β-dihydroperoxide | 67041-44-5

• 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: 5α-cholestane-3α,3β-dihydroperoxide
• 英文别名: 5α-cholestane-3,3-dihydroperoxide；3,3-dihydroperoxy-5α-cholestane；3,3-bis-hydroperoxy-5α-cholestane；3,3-Dihydroperoxycholestan；(5S,8R,9S,10S,13R,14S,17R)-3,3-dihydroperoxy-10,13-dimethyl-17-[(2R)-6-methylheptan-2-yl]-1,2,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene
• CAS: 67041-44-5
• 化学式: C₂₇H₄₈O₄
• 分子量: 436.676
• InChiKey: NCPHEJHCTIOHDA-FHNVJLOUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.7
• 重原子数：
  31
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  58.9
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  5-Alpha-胆甾烷-3-酮 在 双氧水 、 碘 作用下， 以 乙腈 为溶剂， 反应 24.0h， 以51%的产率得到5α-cholestane-3α,3β-dihydroperoxide
  参考文献：
  名称：

  碘对羰基化合物过氧化的影响

  摘要：

  以碘为催化剂，研究了酮和醛的过氧化反应。酮在10摩尔％的碘存在下与30％的过氧化氢水溶液反应，生成乙腈中的宝石二氢过氧化物和甲醇中的氢过氧缩酮。包括雄甾烷-3,17-二酮在内的各种环状酮的加氢过氧化产率为60-98％，而无环酮的转化效率相近。芳香醛也可以在乙腈中以过氧化氢和碘为催化剂，转化为宝石二氢过氧化物，在甲醇中转化为氢过氧缩醛，而脂肪族醛的反应性与未催化反应相同。叔-丁基氢过氧化物以类似方式反应，得到相应的过醚衍生物。还对二氢过氧化的相对动力学进行了研究，根据该动力学，Hammet方程给出的反应常数（ρ）为-2.76，这表明过渡态中强烈的正电荷发展以及再杂交在氢过氧半水合物向宝石转化中的重要作用-二氢过氧化物。在乙腈中，碘催化剂显然能够区分消除羟基，甲氧基和氢过氧基与将水，甲醇和H 2 O 2加至羰基之间。

  DOI：

  10.1021/jo0708745
• 作为试剂：
  描述：

  甲萘醌 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 5α-cholestane-3α,3β-dihydroperoxide 作用下， 以 甲苯 为溶剂， 反应 72.0h， 生成 (2R,3S)-2,3-epoxy-2-methyl-1,4-naphthoquinone 、 (2S,3R)-2,3-epoxy-2-methyl-1,4-naphthoquinone
  参考文献：
  名称：

  Enantioselective epoxidation of 2-substituted 1,4-naphthoquinones using gem-dihydroperoxides

  摘要：

  New gem-dihydroperoxides were successfully used for DBU-promoted enantioselective epoxidation of 2-substituted 1,4-naphtlloquinones. The corresponding 1,4-naphthoquinone epoxides were obtained in yields up to 97% and ee's up to 82%. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2009.05.096

文献信息

• Mild and Efficient Re(VII)-Catalyzed Synthesis of 1,1-Dihydroperoxides
  作者：Prasanta Ghorai、Patrick H. Dussault

  DOI：10.1021/ol801859c

  日期：2008.10.16

  Re2O7 in CH3CN is a remarkably efficient and mild catalyst for the peroxyacetalization of ketones, aldehydes, or acetals by H2O2 to generate 1,1-dihydroperoxides. Me3SiOReO3 and methyl rhenium trioxide (MTO) are also effective catalysts under these reaction conditions.
• Iodine as a Catalyst for Efficient Conversion of Ketones to <i>g</i><i>em</i>-Dihydroperoxides by Aqueous Hydrogen Peroxide
  作者：Katja Žmitek、Marko Zupan、Stojan Stavber、Jernej Iskra

  DOI：10.1021/ol060590r

  日期：2006.6.1

  Iodine has been shown to be an efficient catalyst for the selective dihydroperoxidation of ketones with aqueous hydrogen peroxide. Ketones were directly converted to their corresponding gem-dihydroperoxides using a "green" oxidant (30% aq H2O2) and a simple catalyst ( iodine) under neutral conditions in acetonitrile. The yield of hydroperoxidation of various cyclic ketones was 60-98% including androstane- 3,17-dione, and acyclic ketones were converted with a similar efficiency.
• Oxidation of n-alkyl-n'-tosylhydrazines to hydroperoxides
  作者：L. Caglion、F. Gasparrini、D. Misiti、G. Palmieri

  DOI：10.1016/0040-4020(78)88048-x

  日期：1978.1
• Enantioselective epoxidation of tertiary allylic alcohols by chiral dihydroperoxides
  作者：Alexander Bunge、Hans-Jürgen Hamann、Dennis Dietz、Jürgen Liebscher

  DOI：10.1016/j.tet.2013.01.032

  日期：2013.3

  gem-Dihydroperoxides were successfully used for the enantioselective epoxidation of tertiary and primary allylic alcohols. Epoxides derived from tertiary alcohols were obtained in yields up to 71% with ee's up to 52%. (c) 2013 Elsevier Ltd. All rights reserved.
• Steroidal geminal dihydroperoxides and 1,2,4,5-tetraoxanes: Structure determination and their antimalarial activity
  作者：Nina M. Todorović、Milutin Stefanovic、Bernard Tinant、Jean-Paul Declercq、Michael T. Makler、Bogdan A. S̆olaja

  DOI：10.1016/s0039-128x(96)00203-6

  日期：1996.12

  Cholestane-derived gem-dihydroperoxides and tetraoxanes were synthesized starting from 5 alpha- and 5 beta-cholestan-3-ones by acid-catalyzed addition of hydrogen peroxide to the ketone. They were characterized by IR, NMR, and mass spectroscopy analysis aided by molecular mechanics calculations, and, in the instance of 5 beta-cholestane-3 alpha,3 beta-dihydroperoxide (6), by x-ray analysis. The synthesized compounds were tested in vitro against Plasmodium falciparum Sierra Leone (D6) and Indochina (W2) malaria clones. All compounds were inactive to both clones, with the exception of tetraoxane 7a, which exhibited modest activity toward D6 clone with IC50 = 155 nM. (C) 1996 by Elsevier Science Inc.