5α-hydroperoxy-3β-benzoyloxycholest-6-ene | 129238-78-4

• 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-hydroperoxy-3β-benzoyloxycholest-6-ene
• 英文别名: [(3S,5S,8S,9S,10R,13R,14S,17R)-5-hydroperoxy-10,13-dimethyl-17-[(2R)-6-methylheptan-2-yl]-1,2,3,4,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-3-yl] benzoate
• CAS: 129238-78-4
• 化学式: C₃₄H₅₀O₄
• 分子量: 522.769
• InChiKey: WHFXNCYADAPKLX-WMEVSXJDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.9
• 重原子数：
  38
• 可旋转键数：
  9
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  5α-hydroperoxy-3β-benzoyloxycholest-6-ene 以 氯仿 为溶剂， 反应 72.0h， 生成 7α-hydroperoxy-3β-benzoyloxycholest-5-ene
  参考文献：
  名称：

  Ene reactions of allylically stannylated cholestenes: singlet oxygenation of 7α-triphenylstannylcholest-5-en-3β-ol, and of 7α-triphenylstannyl- and 7α-tributylstannyl-cholest-5-ene-3-one, and the rearrangement of 5α-tributylstannylperoxy-3β-benzoyloxycholest-6-ene and of 7α-tributylstannylperoxy-3β-benzoyloxycholest-5-ene

  摘要：

  The reaction of some allylically stannylated steroids with singlet oxygen has been investigated. 7-alpha-Triphenylstannylcholest-5-ene-3-beta-ol reacts on the beta-face with shift of the 4-beta-hydrogen to give 6-beta-hydroperoxy-7-alpha-triphenylstannylcholest-4-ene-3-beta-ol, whereas cholest-5-ene-3-beta-ol itself reacts on the alpha-face to give 5-alpha-hydroperoxycholest-6-ene-3-beta-ol.7-alpha-Triphenylstannyl- and 7-alpha-tributylstannylcholest-5-ene-3-one give the corresponding 6-beta-hydroperoxy-7-alpha-stannylcholest-4-ene-3-one (50-55%), together with the 4,6-dien-3-one which is formed by elimination. In contrast, the parent cholest-5-en-3-one under the same conditions gives some of the 6-beta-hydroperoxy-4-ene-3-one, but the principal product is the hemiperketal from the 5-alpha-hydroperoxycholest-6-ene-3-one.In neither system was there any evidence for a metalloene reaction, nor for cycloaddition accompanied by a nucleophilic 1,2-shift of the tin.3-beta-Benzoyloxy-5-alpha-tributylstannylperoxycholest-6-ene undergoes the Schenck and Smith types of rearrangement by a radical chain mechanism to give successively the corresponding 7-alpha- and 7-beta-stannylperoxy-5-enes.

  DOI：

  10.1039/p29920001095
• 作为产物：
  描述：

  胆固醇苯甲酸酯 在 hematoporphyrin 作用下， 以 吡啶 为溶剂， 反应 17.0h， 以0.86 g的产率得到5α-hydroperoxy-3β-benzoyloxycholest-6-ene
  参考文献：
  名称：

  Efficient Preparation of Chiral C₂-Symmetrical 2,6,9-Trioxabicyclo[3.3.1]nonanes from Cholesteryl Benzoate

  摘要：

  DOI：

  10.1021/jo961818z

文献信息

• Tritylation, methoxymethylation, and silylation of allylic hydroperoxides via stannyl peroxide intermediates. Allylic rearrangement of a stannyl peroxide
  作者：Richard K. Haynes、Simone C. Vonwiller

  DOI：10.1039/c39900000448

  日期：——

  hydroperoxides are quantitatively converted by tributyltin methoxide into stannyl peroxides, whose treatment with trityl chloride, chloromethyl methyl ether, and t-butyldimethylsilyl trifluoromethane-sulphonate give the corresponding trityl, methoxymethyl, and silyl peroxides, a tertiary allylic hydroperoxide gives rearrangement products on stannylation and treatment with trityl chloride.

  甲基三丁基锡将伯和仲烯丙基氢过氧化物定量地转化成过氧化甲锡，用三苯甲基氯，氯甲基甲基醚和叔丁基二甲基甲硅烷基三氟甲烷磺酸酯处理可得到相应的三苯甲基，甲氧基甲基和甲硅烷基过氧化物，叔烯丙基氢过氧化物则可进行重排甲磺酰化并用三苯甲基氯处理的产品。
• Iron(III)-induced cleavage of cyclic allylic hydroperoxides to dicarbonyl compounds under aprotic conditions
  作者：Richard K. Haynes、Simone C. Vonwiller

  DOI：10.1039/c39900000449

  日期：——

  Secondary and tertiary cyclic allylic hydroperoxides are rapidly cleaved by iron(III) catalysts in dichloromethane into dicarbonyl compounds.

  仲和叔环状烯丙基氢过氧化物被铁（III）催化剂在二氯甲烷中迅速裂解成二羰基化合物。
• HAYNES, RICHARD K.;VONWILLER, SIMONE C., J. CHEM. SOC. CHEM. COMMUN.,(1990) N, C. 449-451
  作者：HAYNES, RICHARD K.、VONWILLER, SIMONE C.

  DOI：——

  日期：——
• Ene reactions of allylically stannylated cholestenes: singlet oxygenation of 7α-triphenylstannylcholest-5-en-3β-ol, and of 7α-triphenylstannyl- and 7α-tributylstannyl-cholest-5-ene-3-one, and the rearrangement of 5α-tributylstannylperoxy-3β-benzoyloxycholest-6-ene and of 7α-tributylstannylperoxy-3β-benzoyloxycholest-5-ene
  作者：H.-S. Dang、Alwyn G. Davies

  DOI：10.1039/p29920001095

  日期：——

  The reaction of some allylically stannylated steroids with singlet oxygen has been investigated. 7-alpha-Triphenylstannylcholest-5-ene-3-beta-ol reacts on the beta-face with shift of the 4-beta-hydrogen to give 6-beta-hydroperoxy-7-alpha-triphenylstannylcholest-4-ene-3-beta-ol, whereas cholest-5-ene-3-beta-ol itself reacts on the alpha-face to give 5-alpha-hydroperoxycholest-6-ene-3-beta-ol.7-alpha-Triphenylstannyl- and 7-alpha-tributylstannylcholest-5-ene-3-one give the corresponding 6-beta-hydroperoxy-7-alpha-stannylcholest-4-ene-3-one (50-55%), together with the 4,6-dien-3-one which is formed by elimination. In contrast, the parent cholest-5-en-3-one under the same conditions gives some of the 6-beta-hydroperoxy-4-ene-3-one, but the principal product is the hemiperketal from the 5-alpha-hydroperoxycholest-6-ene-3-one.In neither system was there any evidence for a metalloene reaction, nor for cycloaddition accompanied by a nucleophilic 1,2-shift of the tin.3-beta-Benzoyloxy-5-alpha-tributylstannylperoxycholest-6-ene undergoes the Schenck and Smith types of rearrangement by a radical chain mechanism to give successively the corresponding 7-alpha- and 7-beta-stannylperoxy-5-enes.
• Efficient Preparation of Chiral <i>C</i>₂-Symmetrical 2,6,9-Trioxabicyclo[3.3.1]nonanes from Cholesteryl Benzoate
  作者：Simone C. Vonwiller

  DOI：10.1021/jo961818z

  日期：1997.2.1