methyl N-(acetoxymethyl)carbamate | 28482-68-0

• 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 N-(acetoxymethyl)carbamate
• 英文别名: N-(acetoxymethyl)carbamate；(Methoxycarbonylamino)methyl acetate
• CAS: 28482-68-0
• 化学式: C₅H₉NO₄
• 分子量: 147.131
• InChiKey: IYFFZCXFWNFPSY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  64.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl N-(acetoxymethyl)carbamate 、 2-三(苯基)膦亚基乙酰胺 在 三乙胺 作用下， 以 甲醇 为溶剂， 以64%的产率得到Carbamic acid, [3-amino-3-oxo-2-(triphenylphosphoranylidene)propyl]-, methyl ester
  参考文献：
  名称：

  New phosphonium ylides by functionalization of triphenylphosphoranylideneacetamide

  摘要：

  Triphenylphosphoranylideneacetamide undergoes Michael reactions with several acceptors, giving rise, apart from the normal Michael adducts, to the formation of different products like glutarimide ylides and stabilized iminophosphoranes. Wittig reactions with these new ylides lead to a variety of alpha,beta-unsaturated carbonyl compounds.

  DOI：

  10.1016/s0040-4039(00)91662-9

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

  DOI：10.1016/s0040-4020(01)86443-7

  日期：1991.1

  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.
• 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.
• New phosphonium ylides by functionalization of triphenylphosphoranylideneacetamide
  作者：Martin J. Wanner、Gerrit-Jan Koomen

  DOI：10.1016/s0040-4039(00)91662-9

  日期：1992.3

  Triphenylphosphoranylideneacetamide undergoes Michael reactions with several acceptors, giving rise, apart from the normal Michael adducts, to the formation of different products like glutarimide ylides and stabilized iminophosphoranes. Wittig reactions with these new ylides lead to a variety of alpha,beta-unsaturated carbonyl compounds.