1-(4-Chloro-butyl)-2-oxo-cyclopentanecarboxylic acid methyl ester | 78073-61-7

• 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: 1-(4-Chloro-butyl)-2-oxo-cyclopentanecarboxylic acid methyl ester
• CAS: 78073-61-7
• 化学式: C₁₁H₁₇ClO₃
• 分子量: 232.707
• InChiKey: HBLVNZKUNNNVGX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.31
• 重原子数：
  15.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  43.37
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  1-(4-Chloro-butyl)-2-oxo-cyclopentanecarboxylic acid methyl ester 在 sodium azide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 2.5h， 生成 2-(4'-叠氮丁基)环戊酮
  参考文献：
  名称：

  Intramolecular Schmidt Reactions of Alkyl Azides with Ketones: Scope and Stereochemical Studies

  摘要：

  The intramolecular Schmidt reaction of alkyl azides and ketones has been demonstrated. The reaction is proposed to occur via initial attack of an azide on a ketone activated by a variety of protic or Lewis acids, including trifluoroacetic acid, titanium tetrachloride, and others. The resulting azidohydrin undergoes a direct rearrangement to afford the product amide and molecular nitrogen. When cyclic ketones are used, fused bicyclic lactams of types encountered in a wide variety of natural products are obtained. Although the distance allowed between the carbonyl group and the alkyl azide is quite restricted, the reaction is general with respect to the ketone component, including acyclic ketones and cyclic substrates ranging from standard to large ring sizes. The reaction also succeeds with aldehydes, although elimination or hydride migration products compete. In several cases examined, the reaction was found to proceed with retention of configuration at the migrating carbon. Competing reactions with beta-diketones and alpha,beta-unsaturated ketones were found to predominate over ring expansion.

  DOI：

  10.1021/ja00147a006
• 作为产物：
  描述：

  1-氯-4-碘丁烷 、 2-甲氧羰基环戊酮 在 盐酸 、 sodium hydride 作用下， 生成 1-(4-Chloro-butyl)-2-oxo-cyclopentanecarboxylic acid methyl ester
  参考文献：
  名称：

  Intramolecular Schmidt Reactions of Alkyl Azides with Ketones: Scope and Stereochemical Studies

  摘要：

  The intramolecular Schmidt reaction of alkyl azides and ketones has been demonstrated. The reaction is proposed to occur via initial attack of an azide on a ketone activated by a variety of protic or Lewis acids, including trifluoroacetic acid, titanium tetrachloride, and others. The resulting azidohydrin undergoes a direct rearrangement to afford the product amide and molecular nitrogen. When cyclic ketones are used, fused bicyclic lactams of types encountered in a wide variety of natural products are obtained. Although the distance allowed between the carbonyl group and the alkyl azide is quite restricted, the reaction is general with respect to the ketone component, including acyclic ketones and cyclic substrates ranging from standard to large ring sizes. The reaction also succeeds with aldehydes, although elimination or hydride migration products compete. In several cases examined, the reaction was found to proceed with retention of configuration at the migrating carbon. Competing reactions with beta-diketones and alpha,beta-unsaturated ketones were found to predominate over ring expansion.

  DOI：

  10.1021/ja00147a006

文献信息

• A new spiro-annelation procedure: intramolecular decarboxylative alkylation of β-keto-esters
  作者：Robert G. Eilerman、Brian J. Willis

  DOI：10.1039/c39810000030

  日期：——

  A new intramolecular decarboxylative alkylation route to spirocyclic ketones, and its application to the synthesis of (±)-β-vetivone and (±)-β-vetispirene are described.

  描述了一种新的分子内脱羧烷基化成螺环酮的路线，及其在合成（±）-β- vetivone和（±）-β- vetispirene中的应用。