Methyl 2-[but-3-enyl(ethoxycarbonyl)amino]-2-hydroxyacetate | 135690-64-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: Methyl 2-[but-3-enyl(ethoxycarbonyl)amino]-2-hydroxyacetate
• CAS: 135690-64-1
• 化学式: C₁₀H₁₇NO₅
• 分子量: 231.249
• InChiKey: AJVGQZSLMPWPEO-UHFFFAOYSA-N

物化性质

• 沸点：
  322.5±42.0 °C(Predicted)
• 密度：
  1.151±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  16
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  76.1
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  Methyl 2-[but-3-enyl(ethoxycarbonyl)amino]-2-hydroxyacetate 在 吡啶 、 4-二甲氨基吡啶 、 三甲基氯硅烷 、 四氯化锡 、 sodium iodide 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 23.0h， 生成 trans-4-chloro-2-piperidinecarboxylic 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：

  ethyl N-(3-butenyl)carbamate 、 methyl glyoxylate hydrate 以 苯 为溶剂， 反应 3.0h， 以80%的产率得到Methyl 2-[but-3-enyl(ethoxycarbonyl)amino]-2-hydroxyacetate
  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

• Formic acid-induced π-cyclization of glycine cation equivalents to substituted pipecolic acid derivatives
  作者：Peter M Esch、de Boer F Richard、Hiemstra Henk、Ilona M Boska、Speckamp W. Nico

  DOI：10.1016/s0040-4020(01)86444-9

  日期：1991.1

  Formic acid-mediated cyclization reactions of N-(3-alkenyl)-N-(methoxycarbonyl)-acetoxyglycine esters are described. The major reaction products are 4-formyloxypipecolic acid derivatives, formed with low stereoselectivity at C-4. The several subtle features of the cyclization process are satisfactorily explained by a mechanism involving (1) a rapid cationic aza-Cope rearrangement of the incipient iminium ion and (2) participation of the ester moiety through formation of a relatively stable bicyclic dioxycarbenium cation as pivotal intermediate.