acetoxyacetic acid methyl ester | 126774-14-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: acetoxyacetic acid methyl ester
• 英文别名: acetoxyacetic acid methyl ester；methyl 2-acetyloxy-2-[[(E)-hex-3-enyl]-methoxycarbonylamino]acetate
• CAS: 126774-14-9
• 化学式: C₁₃H₂₁NO₆
• 分子量: 287.313
• InChiKey: VCHHZTYHLTYEMF-VOTSOKGWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  20
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  82.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  acetoxyacetic acid methyl ester 在 盐酸 、 四氯化锡 、 碳酸氢钠 作用下， 反应 20.0h， 生成 rel-(2R,3R,4S)-3-ethyl-4-hydroxy-2-piperidinecarboxylic acid
  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：

  反式-3-己烯-1-醇 在 吡啶 、 4-二甲氨基吡啶 、 sodium azide 、 水 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 42.75h， 生成 acetoxyacetic 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

• Reductive cyclization of carbon-centered glycine radicals; a novel synthetic route to cyclic α-amino acids
  作者：Peter M. Esch、Henk Hiemstra、Richard F. de Boer、W.Nico Speckamp

  DOI：10.1016/s0040-4020(01)81240-0

  日期：1992.1

  Reductive cyclizations (tributylin hydride, AIBN) of several α-(penthylthio)glycine derivatives with a 30alkenyl 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. Such radicals can be considered as relatively stable captodative radicals, but are reactive

  报道了几种在氮上具有30个烯基取代基的α-（苯硫基）甘氨酸衍生物的还原环化作用（氢化三丁基氢化物，AIBN）。这些反应通过2-氮杂-5-烯-1-基作为中间体进行，该中间体在自由基中心和氮上带有吸电子羰基取代基。这样的基团可以被认为是相对稳定的Capdudative基团，但是对于烯烃环化而言是足够反应性的。主要产物通常来自5- exo环化，是脯氨酸在结构上令人关注的类似物。经由6-哌啶酸类似物的不同量的内切在某些情况下，也可以得到环化。乙炔的类似环化是成功的，而腈则不能环化。
• ESCH, PETER M.;HIEMSTRA, HENK;SPECKAMP, W. NICO, TETRAHEDRON LETT., 31,(1990) N, C. 759-762
  作者：ESCH, PETER M.、HIEMSTRA, HENK、SPECKAMP, W. NICO

  DOI：——

  日期：——
• ESCH, PETER M.;BOSKA, ILONA M.;HIEMSTRA, HENK;, SPECKAMP W. NICO, SYNLETT.,(1989) N, C. 38-40
  作者：ESCH, PETER M.、BOSKA, ILONA M.、HIEMSTRA, HENK、, SPECKAMP W. NICO

  DOI：——

  日期：——