7α-triphenylstannylcholesta-5-ene-3-one | 143657-29-8

• 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: 7α-triphenylstannylcholesta-5-ene-3-one
• CAS: 143657-29-8
• 化学式: C₄₅H₅₈OSn
• 分子量: 733.665
• InChiKey: ZYMAMPQBVYPQIO-VPCCLFBTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.49
• 重原子数：
  47
• 可旋转键数：
  5
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.51
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  7α-triphenylstannylcholesta-5-ene-3-one 在 air 、 tetraphenylporphyrin 作用下， 以 二氯甲烷 为溶剂， 生成 4,6-胆固醇二烯-3-酮
  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

文献信息

• 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.