[(1S,4R,5S,8S,9S,12S,13R,17R,18R,22S)-9,13-dimethyl-16-oxo-8-hexacyclo[11.9.0.01,17.04,12.05,9.018,22]docosanyl] acetate | 131105-30-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子
• 英文名称: [(1S,4R,5S,8S,9S,12S,13R,17R,18R,22S)-9,13-dimethyl-16-oxo-8-hexacyclo[11.9.0.01,17.04,12.05,9.018,22]docosanyl] acetate
• CAS: 131105-30-1；131176-85-7；131176-86-8
• 化学式: C₂₆H₃₈O₃
• 分子量: 398.586
• InChiKey: AYZNVZUJKXYUEG-XHPAMCINSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.56
• 重原子数：
  29.0
• 可旋转键数：
  1.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  43.37
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为产物：
  描述：

  [(1S,4R,5S,8S,9S,12S,13R,17S,18R,22S)-9,13-dimethyl-16-oxo-8-hexacyclo[11.9.0.01,17.04,12.05,9.018,22]docosanyl] acetate 在 吡啶 、 氢氧化钾 、 乙酸酐 作用下， 生成 [(1S,4R,5S,8S,9S,12S,13R,17R,18R,22S)-9,13-dimethyl-16-oxo-8-hexacyclo[11.9.0.01,17.04,12.05,9.018,22]docosanyl] acetate
  参考文献：
  名称：

  Stereochemistry of [2 + 2] photocycloaddition of cyclic enones to alkenes: structural and mechanistic considerations in formation of trans-fused cycloadducts

  摘要：

  Photocycloaddition of 2-cyclohexenone to cyclopentene gives four [2 + 2] adducts, rather than only two as reported previously. Differentiation between the cis-anti-cis and cis-syn-cis structures was made on the basis of differences in C-13 chemical shifts in the two isomers. The structures of the two trans-fused adducts, which were not isolated, derive from their base-catalyzed epimerization to the corresponding cis-fused isomers. One trans-fused and one cis-fused cycloadduct are formed initially in a ratio of 2:1, respectively, upon photoaddition of testosterone acetate to cyclopentene, but this ratio changes in favor of the cis-fused isomer as the irradiation progresses due to secondary reactions. These adducts were identified by X-ray crystallography as the trans-fused (4alpha,5beta) and cis-fused (4alpha,5alpha) structures. Epimerization of the trans-fused adduct in base led to isolation of the alternative cis-fused adduct (4beta,5beta) whose X-ray crystal structure was also determined. The X-ray structure of the oxime of the trans-fused photoadduct of 2-cyclohexenone and tetramethylethylene was also obtained for structural comparison with the steroid enone adducts. These are believed to be the first definitive structure determinations of trans-fused bicyclo[4.2.0]octan-2-ones. The assignments of H-1 NMR coupling constants to vicinal cis and trans protons on the cyclobutane ring are based on the relevant dihedral angles obtained from the X-ray structures and from molecular modeling. Mechanisms for the formation of trans-fused adducts from both planar and twisted cyclohexenone triplets are discussed.

  DOI：

  10.1021/jo00002a016

文献信息

• SCHUSTER, DAVID I.;KAPRINIDIS, NIKOLAS;WINK, DONALD J.;DEWAN, JOHN C., J. ORG. CHEM., 56,(1991) N, C. 561-567
  作者：SCHUSTER, DAVID I.、KAPRINIDIS, NIKOLAS、WINK, DONALD J.、DEWAN, JOHN C.

  DOI：——

  日期：——