3-chloromethyl-pyrrolidine-1,2-dicarboxylic acid dimethyl ester

• 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: 3-chloromethyl-pyrrolidine-1,2-dicarboxylic acid dimethyl ester
• 英文别名: Dimethyl 3-(chloromethyl)pyrrolidine-1,2-dicarboxylate
• 化学式: C₉H₁₄ClNO₄
• 分子量: 235.667
• InChiKey: HHWKCAQLMOMLRE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  55.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3-chloromethyl-pyrrolidine-1,2-dicarboxylic acid dimethyl ester 在 氢氧化钾 作用下， 以 甲醇 为溶剂， 反应 18.0h， 以88%的产率得到(2R*,3S*)-3-chloromethyl-pyrrolidine-1,2-dicarboxylic acid 1-methyl ester
  参考文献：
  名称：

  Transition metal-catalyzed chlorine transfer cyclizations of carbon-centered glycine radicals; A novel synthetic route to cyclic α-amino acids

  摘要：

  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.

  DOI：

  10.1016/s0040-4020(01)80863-2
• 作为产物：
  描述：

  methyl N-(3-butenyl)carbamate 在 copper(l) chloride 2,2'-联吡啶 、 五氯化磷 作用下， 以 四氯化碳 、 1,2-二氯乙烷 、 苯 为溶剂， 反应 19.25h， 生成 3-chloromethyl-pyrrolidine-1,2-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  铜催化甘氨酸和乙醇酸衍生物的氯转移环化

  摘要：

  在催化量的氯化亚铜和2,2'-联吡啶的存在下，氯甘氨酸和氯乙醇酸衍生物可在原子转移过程中平稳环化，分别生成官能化的脯氨酸酯和2-四氢呋喃羧酸酯。

  DOI：

  10.1016/0040-4039(91)80706-c

文献信息

• Changing stereoselectivity and regioselectivity in copper(<scp>i</scp>)-catalyzed 5-<i>exo</i> cyclization by chelation and rigidity in aminoalkyl radicals: synthesis towards diverse bioactive N-heterocycles
  作者：Sandhya Sadanandan、Dharmendra Kumar Gupta

  DOI：10.1039/c9nj05166j

  日期：——

  Chelation, rigidity and carbon-radical positions in aminoalkyl precursors disturb the usual 2,4-trans diastereoselectivity and 5-exo mode in Cu(i)-catalyzed ATRC.

  螯合、刚性和氨基烷基前体中的碳自由基位置会干扰通常的2,4-trans 反式选择性和5-exo 模式在Cu(i)-催化的ATRC中。
• Copper catalyzed chlorine transfer cyclizations of glycine and glycolic acid derivatives
  作者：Jan H. Udding、Henk Hiemstra、Marco N.A. van Zanden、W.Nico Speckamp

  DOI：10.1016/0040-4039(91)80706-c

  日期：1991.6

  Chloroglycine and chloroglycolic acid derivatives smoothly cyclize in the presence of a catalytic amount of cuprous chloride and 2,2′-bipyridine to produce functionalized proline and 2-tetrahydrofurancarboxylic esters, respectively, in an atom transfer process.

  在催化量的氯化亚铜和2,2'-联吡啶的存在下，氯甘氨酸和氯乙醇酸衍生物可在原子转移过程中平稳环化，分别生成官能化的脯氨酸酯和2-四氢呋喃羧酸酯。
• 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.