4',4'-dimethylspiro<1,3-dioxolane-2,3'-cholest-5'-en-7'-one> | 173354-36-4

• 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: 4',4'-dimethylspiro<1,3-dioxolane-2,3'-cholest-5'-en-7'-one>
• 英文别名: (8S,9S,10R,13R,14S,17R)-4,4,10,13-tetramethyl-17-[(2R)-6-methylheptan-2-yl]spiro[1,2,8,9,11,12,14,15,16,17-decahydrocyclopenta[a]phenanthrene-3,2'-1,3-dioxolane]-7-one
• CAS: 173354-36-4
• 化学式: C₃₁H₅₀O₃
• 分子量: 470.736
• InChiKey: DNIYRCQCEGSOSW-FTZFMMGGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.4
• 重原子数：
  34
• 可旋转键数：
  5
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4',4'-dimethylspiro<1,3-dioxolane-2,3'-cholest-5'-en-7'-one> 在 吡啶 、 盐酸 、 氨 、 lithium 、 sodium tert-pentoxide 、 L-Selectride 、 叔丁醇 作用下， 以 四氢呋喃 、 乙醚 、 丙酮 、 甲苯 为溶剂， 反应 7.34h， 生成 (5α,7α)-4,4,7-trimethylcholest-2-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：

  4',4'-dimethylspiro<1,3-dioxolane-2,3'-cholest-5'-ene> 在 重铬酸吡啶 、 3 A molecular sieve 作用下， 以 吡啶 为溶剂， 反应 2.0h， 以87%的产率得到4',4'-dimethylspiro<1,3-dioxolane-2,3'-cholest-5'-en-7'-one>
  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.