(1aR,1bS,2aR,5aR,7aS)-4,4-Dimethyl-hexahydro-1,3,5-trioxa-6a-aza-cyclopropa[a]-s-indacen-6-one

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚里西啶
• 英文名称: (1aR,1bS,2aR,5aR,7aS)-4,4-Dimethyl-hexahydro-1,3,5-trioxa-6a-aza-cyclopropa[a]-s-indacen-6-one
• 英文别名: (3R,7R,9S,10R,12S)-5,5-dimethyl-4,6,11-trioxa-1-azatetracyclo[7.4.0.03,7.010,12]tridecan-2-one
• 化学式: C₁₁H₁₅NO₄
• 分子量: 225.244
• InChiKey: LAEFBLJGOTXOJK-KVEIKIFDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  51.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  3,5,6,7,8,8a-Hexahydro-6,7-(isopropylidenedioxy)-5-oxoindolizine 在 sodium dihydrogenphosphate 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 (1aS,1bS,2aR,5aR,7aR)-4,4-Dimethyl-hexahydro-1,3,5-trioxa-6a-aza-cyclopropa[a]-s-indacen-6-one 、 (1aR,1bS,2aR,5aR,7aS)-4,4-Dimethyl-hexahydro-1,3,5-trioxa-6a-aza-cyclopropa[a]-s-indacen-6-one
  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