α-hydroxy-2-oxo-5-(2-propenyl)-1-pyrrolidineacetic acid methyl ester | 158212-97-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: α-hydroxy-2-oxo-5-(2-propenyl)-1-pyrrolidineacetic acid methyl ester
• 英文别名: (2-allyl-5-oxo-pyrrolidin-1-yl)-hydroxy-acetic acid methyl ester
• CAS: 158212-97-6
• 化学式: C₁₀H₁₅NO₄
• 分子量: 213.233
• InChiKey: NVDZDGQHFOQCAZ-UHFFFAOYSA-N

物化性质

• 沸点：
  375.5±32.0 °C(predicted)
• 密度：
  1.194±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.04
• 重原子数：
  15.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  66.84
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  α-hydroxy-2-oxo-5-(2-propenyl)-1-pyrrolidineacetic acid methyl ester 在 吡啶 、 4-二甲氨基吡啶 、 四氯化锡 作用下， 以 二氯甲烷 为溶剂， 反应 21.0h， 生成 (5R*,7R*,8aS*)-7-chloro-3-oxo-octahydro-indolizine-5-carboxylic acid methyl ester
  参考文献：
  名称：

  Tin tetrachloride-induced π-cyclizations of glycine cation equivalents to substituted pipecolic acid derivatives

  摘要：

  Cationic pi-cyclization reactions of N-(3-alkenyl)-N-(methoxycarbonyl)acetoxyglycine esters induced by tin tetrachloride in dichloromethane are described. Reactions started and quenched with water at -78-degrees-C mainly yield cis-4-hydroxypipecolic esters, whereas reactions quenched after warm-up to room temperature provide trans-4-chloropipecolic esters as major products. A mechanistic scheme is advanced which adequately explains these results. The essentials are a rapid cationic aza-Cope equilibrium of the incipient iminium cation, and participation of the ester moiety through formation of a relatively stable bicyclic dioxycarbenium cation as pivotal intermediate.

  DOI：

  10.1016/s0040-4020(01)86443-7
• 作为产物：
  描述：

  methyl glyoxylate hydrate 、 5-allylpyrrolidin-2-one 以 苯 为溶剂， 反应 3.0h， 以86%的产率得到α-hydroxy-2-oxo-5-(2-propenyl)-1-pyrrolidineacetic acid methyl ester
  参考文献：
  名称：

  Tin tetrachloride-induced π-cyclizations of glycine cation equivalents to substituted pipecolic acid derivatives

  摘要：

  Cationic pi-cyclization reactions of N-(3-alkenyl)-N-(methoxycarbonyl)acetoxyglycine esters induced by tin tetrachloride in dichloromethane are described. Reactions started and quenched with water at -78-degrees-C mainly yield cis-4-hydroxypipecolic esters, whereas reactions quenched after warm-up to room temperature provide trans-4-chloropipecolic esters as major products. A mechanistic scheme is advanced which adequately explains these results. The essentials are a rapid cationic aza-Cope equilibrium of the incipient iminium cation, and participation of the ester moiety through formation of a relatively stable bicyclic dioxycarbenium cation as pivotal intermediate.

  DOI：

  10.1016/s0040-4020(01)86443-7

文献信息

• Transition metal-catalyzed chlorine transfer cyclizations of carbon-centered glycine radicals; A novel synthetic route to cyclic α-amino acids
  作者：Jan H. Udding、C. (Kees) J.M. Tuijp、Henk Hiemstra、W. Nico Speckamp

  DOI：10.1016/s0040-4020(01)80863-2

  日期：1994.1

  Copper(I)-catalyzed chlorine transfer radical cyclizations of several alpha-chloroglycine derivatives with a 3-alkenyl substituent at nitrogen are reported. These reactions proceed via 2-aza-5-alken-1-yl radicals as intermediates which bear electron-withdrawing carbonyl substituents at the radical center and at nitrogen. These radicals can be considered as relatively stable captodative radicals, which are easily generated in the presence of Cu(bpy)Cl, but are reactive enough for olefin cyclization. The main products usually arise from 5-exo cyclization and are structurally interesting analogues of proline. An X-ray crystal structure of one of the cyclization products is presented.