(3β,5α)-3-hydroxycholestan-7-one methanesulfonate | 173354-55-7

• 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: (3β,5α)-3-hydroxycholestan-7-one methanesulfonate
• 英文别名: [(3S,5R,8R,9S,10S,13R,14S,17R)-10,13-dimethyl-17-[(2R)-6-methylheptan-2-yl]-7-oxo-1,2,3,4,5,6,8,9,11,12,14,15,16,17-tetradecahydrocyclopenta[a]phenanthren-3-yl] methanesulfonate
• CAS: 173354-55-7
• 化学式: C₂₈H₄₈O₄S
• 分子量: 480.753
• InChiKey: KIRGYZNBXROMAF-LOPWXWOVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.8
• 重原子数：
  33
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.96
• 拓扑面积：
  68.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (3β,5α)-3-hydroxycholestan-7-one methanesulfonate 在 sodium tert-pentoxide 作用下， 以 乙醚 、 甲苯 为溶剂， 反应 0.19h， 生成 (5α,7α)-7-methylcholest-3-en-7-ol
  参考文献：
  名称：

  Chemical Consequences of Long-Range Orbital Interactions in Cholestane-3,7-diol Monosulfonate Esters. A Seven-Center Fragmentation

  摘要：

  The manifestation of through-five-bond interactions in the reactions of the rigid 1,5-diol monosulfonate esters (1-3), having an ideal all-trans geometry of the sigma-relay, with sodium tert-amylate is investigated. It has been shown that the deprotonation of the alcohol group in 2 and 3, which results in an increased electrofugal ability of this group, finds expression in a seven-center fragmentation. This fragmentation also illustrates that effective through-five-bond interactions exist between the alcoholate group and the carbocationic center which is generated during the heterolysis. The reaction outcome of mesylate 1 does not indicate effective through-bond interactions, and only elimination is observed. This difference can be attributed to the alkyl substituents on the gamma- and alpha-positions to the mesylate group in 2 and 3, respectively, which stimulate the seven-center fragmentation. Though a reasonable amount of fragmentation product is obtained from 3, the through-five-bond interaction is not strong enough to dominate the reaction course completely and typical El-like processes, i.e., elimination and rearrangement, are competitive. As expected, only a 1,2 Me-shift is observed in the reaction of the axial mesylate 4 where a gauche interaction is present in the geometry of the sigma-relay. The presence of through-bond interactions in the reactions of 3 and 4 becomes apparent by comparison of the reactivity of 3 and 4 with their O-silylated analogs 5 and 6.

  DOI：

  10.1021/jo951655z
• 作为产物：
  描述：

  3β-hydroxy-5α-cholestan-7-one 、 甲基磺酰氯 在 吡啶 作用下， 反应 18.0h， 以45%的产率得到(3β,5α)-3-hydroxycholestan-7-one methanesulfonate
  参考文献：
  名称：

  Chemical Consequences of Long-Range Orbital Interactions in Cholestane-3,7-diol Monosulfonate Esters. A Seven-Center Fragmentation

  摘要：

  The manifestation of through-five-bond interactions in the reactions of the rigid 1,5-diol monosulfonate esters (1-3), having an ideal all-trans geometry of the sigma-relay, with sodium tert-amylate is investigated. It has been shown that the deprotonation of the alcohol group in 2 and 3, which results in an increased electrofugal ability of this group, finds expression in a seven-center fragmentation. This fragmentation also illustrates that effective through-five-bond interactions exist between the alcoholate group and the carbocationic center which is generated during the heterolysis. The reaction outcome of mesylate 1 does not indicate effective through-bond interactions, and only elimination is observed. This difference can be attributed to the alkyl substituents on the gamma- and alpha-positions to the mesylate group in 2 and 3, respectively, which stimulate the seven-center fragmentation. Though a reasonable amount of fragmentation product is obtained from 3, the through-five-bond interaction is not strong enough to dominate the reaction course completely and typical El-like processes, i.e., elimination and rearrangement, are competitive. As expected, only a 1,2 Me-shift is observed in the reaction of the axial mesylate 4 where a gauche interaction is present in the geometry of the sigma-relay. The presence of through-bond interactions in the reactions of 3 and 4 becomes apparent by comparison of the reactivity of 3 and 4 with their O-silylated analogs 5 and 6.

  DOI：

  10.1021/jo951655z

文献信息

• Chemical Consequences of Long-Range Orbital Interactions in Cholestane-3,7-diol Monosulfonate Esters. A Seven-Center Fragmentation
  作者：Petrus M. F. M. Bastiaansen、Ladislav Kohout、Maarten A. Posthumus、Joannes B. P. A. Wijnberg、Aede de Groot

  DOI：10.1021/jo951655z

  日期：1996.1.1

  The manifestation of through-five-bond interactions in the reactions of the rigid 1,5-diol monosulfonate esters (1-3), having an ideal all-trans geometry of the sigma-relay, with sodium tert-amylate is investigated. It has been shown that the deprotonation of the alcohol group in 2 and 3, which results in an increased electrofugal ability of this group, finds expression in a seven-center fragmentation. This fragmentation also illustrates that effective through-five-bond interactions exist between the alcoholate group and the carbocationic center which is generated during the heterolysis. The reaction outcome of mesylate 1 does not indicate effective through-bond interactions, and only elimination is observed. This difference can be attributed to the alkyl substituents on the gamma- and alpha-positions to the mesylate group in 2 and 3, respectively, which stimulate the seven-center fragmentation. Though a reasonable amount of fragmentation product is obtained from 3, the through-five-bond interaction is not strong enough to dominate the reaction course completely and typical El-like processes, i.e., elimination and rearrangement, are competitive. As expected, only a 1,2 Me-shift is observed in the reaction of the axial mesylate 4 where a gauche interaction is present in the geometry of the sigma-relay. The presence of through-bond interactions in the reactions of 3 and 4 becomes apparent by comparison of the reactivity of 3 and 4 with their O-silylated analogs 5 and 6.