methyl (1R,2R,5S,6R,8R,9S,10R,11S,12S)-5,12-diacetyloxy-11-methyl-16-oxospiro[15-oxapentacyclo[9.3.2.15,8.01,10.02,8]heptadec-13-ene-6,2'-oxirane]-9-carboxylate | 123287-95-6

• 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: methyl (1R,2R,5S,6R,8R,9S,10R,11S,12S)-5,12-diacetyloxy-11-methyl-16-oxospiro[15-oxapentacyclo[9.3.2.15,8.01,10.02,8]heptadec-13-ene-6,2'-oxirane]-9-carboxylate
• CAS: 123287-95-6
• 化学式: C₂₄H₂₈O₉
• 分子量: 460.481
• InChiKey: KBJRXDYWLVAQJU-YOJBMTDQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  33
• 可旋转键数：
  6
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  118
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为产物：
  描述：

  3,13-di-O-acetylgibberellic acid methyl ester 在 氧气 、 联苯甲酰 作用下， 以 苯 为溶剂， 反应 1.0h， 以94%的产率得到methyl (1R,2R,5S,6R,8R,9S,10R,11S,12S)-5,12-diacetyloxy-11-methyl-16-oxospiro[15-oxapentacyclo[9.3.2.15,8.01,10.02,8]heptadec-13-ene-6,2'-oxirane]-9-carboxylate
  参考文献：
  名称：

  Efficient and Stereoselective β-Epoxidation of the 16(17)-Double Bond of Gibberellic Acid Derivatives with an Acylperoxy Radical Generated by Irradiation of α-Diketones and Oxygen

  摘要：

  Irradiation of gibberellic acid derivatives in the presence of alpha -diketones in an oxygen saturated solution led to efficient epoxidation of the 16(17)-double bond to give the 16 beta ,17-epoxides predominantly. The observed stereoselectivity of alpha- to beta -epoxidation ranging from 0:100 on 3,13-di-O-acetylgibberellic acid methyl ester (7) through 11:89 on its 3,13-di-O-methoxymethyl congener, i.e., beta -selectivity, was in contrast to the alpha -selectivity of 74:26 resulted from a peracid epoxidation on 7. This clearly illustrates the radical reaction mechanism involving an acylperoxy radical as a one-oxygen transfer species, in which the stability of the diastereomeric transition states of the intermediary alpha -acylperoxy carbon radical determines the stereochemical course.

  DOI：

  10.3987/com-00-s(i)39

文献信息

• Avent, Anthony G.; Baynham, Mark K.; Hanson, James R., Journal of the Chemical Society. Perkin transactions I, 1989, p. 627 - 632
  作者：Avent, Anthony G.、Baynham, Mark K.、Hanson, James R.、Hitchcock, Peter B.、Oliveira, Bras. H. de

  DOI：——

  日期：——