(1R,2R,8aS)-1,2-Bis(benzoyloxy)-5-oxoindolizidine

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (1R,2R,8aS)-1,2-Bis(benzoyloxy)-5-oxoindolizidine
• 英文别名: [(1R,2R,8aS)-1-benzoyloxy-5-oxo-2,3,6,7,8,8a-hexahydro-1H-indolizin-2-yl] benzoate
• 化学式: C₂₂H₂₁NO₅
• 分子量: 379.412
• InChiKey: UKAWRLPRQDLJLL-NLWGTHIKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  72.9
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  苯甲酰氯 、 1,2-Epoxy-5-oxoindolizidine 在 4-二甲氨基吡啶 吡啶 、 硫酸 作用下， 生成 (1S,2S,8aS)-1,2-Bis(benzoyloxy)-5-oxoindolizidine 、 (1S,2S,8aR)-1,2-Bis(benzoyloxy)-5-oxoindolizidine 、 (1R,2R,8aS)-1,2-Bis(benzoyloxy)-5-oxoindolizidine 、 (1R,2R,8aR)-1,2-Bis(benzoyloxy)-5-oxoindolizidine
  参考文献：
  名称：

  Regio- and Stereoselective Functionalization of an Optically Active Tetrahydroindolizine Derivative. Catalytic Asymmetric Syntheses of Lentiginosine, 1,2-Diepilentiginosine, and Gephyrotoxin 209D

  摘要：

  To demonstrate the usefulness of optically active 3,5,8,8a-tetrahydro-5-oxoindolizine (9) which is prepared by the catalytic asymmetric Heck-type cyclization, regio- and stereoselective functionalizations of(S)- and (R)-9 have been examined. Stereoselective epoxidation of 3,5,6,7,8,8a-hexahydro-5-oxoindolizine (10) obtained by the regioselective reduction was examined, and it was found that electrophile (peracid or bromonium cation) reacted from the opposite side of C-8a-H in a highly stereoselective manner. The catalytic asymmetric syntheses of lentiginosine (3) and 1,2-diepilentiginosine (4) using these stereoselective epoxidations have been achieved. Dihydroxylation of(S)-9 catalyzed by OsO4 gave (6R,7R,8aS)-3,5,6,7,8,8a-hexahydro-6,7-d (16) regio- and stereoselectively. Several other functionalizations and a synthesis of gephyrotoxin 209D (6) are also described. The origin of the high stereoselectivity observed in the functionalization of 9 is discussed based on the stereoelectronic principle such as the Cieplak model.

  DOI：

  10.1021/jo00107a019

文献信息

• Regio- and Stereoselective Functionalization of an Optically Active Tetrahydroindolizine Derivative. Catalytic Asymmetric Syntheses of Lentiginosine, 1,2-Diepilentiginosine, and Gephyrotoxin 209D
  作者：Seiji Nukui、Mikiko Sodeoka、Hiroaki Sasai、Masakatsu Shibasaki

  DOI：10.1021/jo00107a019

  日期：1995.1

  To demonstrate the usefulness of optically active 3,5,8,8a-tetrahydro-5-oxoindolizine (9) which is prepared by the catalytic asymmetric Heck-type cyclization, regio- and stereoselective functionalizations of(S)- and (R)-9 have been examined. Stereoselective epoxidation of 3,5,6,7,8,8a-hexahydro-5-oxoindolizine (10) obtained by the regioselective reduction was examined, and it was found that electrophile (peracid or bromonium cation) reacted from the opposite side of C-8a-H in a highly stereoselective manner. The catalytic asymmetric syntheses of lentiginosine (3) and 1,2-diepilentiginosine (4) using these stereoselective epoxidations have been achieved. Dihydroxylation of(S)-9 catalyzed by OsO4 gave (6R,7R,8aS)-3,5,6,7,8,8a-hexahydro-6,7-d (16) regio- and stereoselectively. Several other functionalizations and a synthesis of gephyrotoxin 209D (6) are also described. The origin of the high stereoselectivity observed in the functionalization of 9 is discussed based on the stereoelectronic principle such as the Cieplak model.