(5'α)-4',4'-dimethylspiro<1,3-dioxolane-2,3'-cholestan-7'-one> | 173354-39-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (5'α)-4',4'-dimethylspiro<1,3-dioxolane-2,3'-cholestan-7'-one>
• 英文别名: (5R,8S,9S,10R,13R,14S,17R)-4,4,10,13-tetramethyl-17-[(2R)-6-methylheptan-2-yl]spiro[1,2,5,6,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthrene-3,2'-1,3-dioxolane]-7-one
• CAS: 173354-39-7
• 化学式: C₃₁H₅₂O₃
• 分子量: 472.752
• InChiKey: NHIRFKIVXSUFPA-MZISSAAUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.6
• 重原子数：
  34
• 可旋转键数：
  5
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.97
• 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：

  (5'α)-4',4'-dimethylspiro<1,3-dioxolane-2,3'-cholestan-7'-one> 在 盐酸 、 L-Selectride 作用下， 以 四氢呋喃 、 乙醚 、 丙酮 为溶剂， 反应 7.0h， 生成 (3R,5R,7R,8S,9S,10R,13R,14S,17R)-17-((R)-1,5-Dimethyl-hexyl)-4,4,7,10,13-pentamethyl-hexadecahydro-cyclopenta[a]phenanthrene-3,7-diol
  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'-en-7'-one> 在 氨 、 lithium 、 叔丁醇 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 以90%的产率得到(5'α)-4',4'-dimethylspiro<1,3-dioxolane-2,3'-cholestan-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