Methyl cis-6-chloro-2-hexenoate | 152668-34-3

• 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: Methyl cis-6-chloro-2-hexenoate
• 英文别名: methyl (Z)-6-chlorohex-2-enoate
• CAS: 152668-34-3
• 化学式: C₇H₁₁ClO₂
• 分子量: 162.616
• InChiKey: KKTDRMSDCIROTM-HYXAFXHYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.73
• 重原子数：
  10.0
• 可旋转键数：
  4.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  Methyl cis-6-chloro-2-hexenoate 在 氯化二乙基铝 、 sodium iodide 作用下， 以 丙酮 、 甲苯 为溶剂， 反应 15.0h， 生成 (1R^*,2S^*)-Methyl 4,5-dimethyl-2-(3-iodopropyl)-4-cyclohexenecarboxylate
  参考文献：
  名称：

  Intramolecular nucleophilic acyl substitution reactions of halo-substituted esters and lactones. New applications of organosamarium reagents

  摘要：

  Intramolecular nucleophilic acyl substitution reactions involving a broad range of halo substituted carboxylic acid derivatives have been accomplished in excellent yield employing samarium(II) iodide as the reductive coupling agent. Although particular substrates cyclized most effectively in THF in the presence of tripiperidinophosphine oxide, carboxylic acid esters, the focus of this report, cyclize equally well without such an additive in the presence of a catalytic quantity of iron(III) complexes. Thus a comprehensive series of halo substituted esters were cyclized in excellent yield to the corresponding 4-, 5-, and 6-membered carbocycles. The reaction is extremely mild and selective as demonstrated by experiments wherein alkyl chlorides, acetals, and olefins remain completely intact under the reaction conditions. In addition to introducing a convenient procedure for preparing stereodefined spirocyclic systems, a new ring expansion sequence has been developed that appears extremely general for the preparation of various ring systems.

  DOI：

  10.1021/jo00077a053
• 作为产物：
  描述：

  Methyl 6-chloro-2-hexynoate 在 bis(cyclohexanyl)borane 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以61%的产率得到Methyl cis-6-chloro-2-hexenoate
  参考文献：
  名称：

  Intramolecular nucleophilic acyl substitution reactions of halo-substituted esters and lactones. New applications of organosamarium reagents

  摘要：

  Intramolecular nucleophilic acyl substitution reactions involving a broad range of halo substituted carboxylic acid derivatives have been accomplished in excellent yield employing samarium(II) iodide as the reductive coupling agent. Although particular substrates cyclized most effectively in THF in the presence of tripiperidinophosphine oxide, carboxylic acid esters, the focus of this report, cyclize equally well without such an additive in the presence of a catalytic quantity of iron(III) complexes. Thus a comprehensive series of halo substituted esters were cyclized in excellent yield to the corresponding 4-, 5-, and 6-membered carbocycles. The reaction is extremely mild and selective as demonstrated by experiments wherein alkyl chlorides, acetals, and olefins remain completely intact under the reaction conditions. In addition to introducing a convenient procedure for preparing stereodefined spirocyclic systems, a new ring expansion sequence has been developed that appears extremely general for the preparation of various ring systems.

  DOI：

  10.1021/jo00077a053

文献信息

• Efficient Stereoselective Syntheses of Constrained Glutamates via Michael-Induced Ring Closing Reactions
  作者：Christian Schmidt、Uli Kazmaier

  DOI：10.1002/ejoc.200700965

  日期：2008.2

  ester enolates are highly efficient nucleophiles for the synthesis of conformationally constrained glutamates via domino sequences of Michael additions and subsequent ring closures (MIRC). This protocol allows the generation of 3–6-membered ring systems in high yields and excellent diastereoselectivities. Depending on the reaction conditions either carbocyclic or heterocyclic ring systems are obtained.

  锌螯合甘氨酸酯烯醇化物是一种高效的亲核试剂，用于通过迈克尔加成和随后的闭环 (MIRC) 的多米诺骨牌序列合成构象受限的谷氨酸。该协议允许以高产率和出色的非对映选择性生成 3-6 元环系统。根据反应条件，可以获得碳环或杂环系统。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
• Intramolecular nucleophilic acyl substitution reactions of halo-substituted esters and lactones. New applications of organosamarium reagents
  作者：Gary A. Molander、Jeffrey A. McKie

  DOI：10.1021/jo00077a053

  日期：1993.12

  Intramolecular nucleophilic acyl substitution reactions involving a broad range of halo substituted carboxylic acid derivatives have been accomplished in excellent yield employing samarium(II) iodide as the reductive coupling agent. Although particular substrates cyclized most effectively in THF in the presence of tripiperidinophosphine oxide, carboxylic acid esters, the focus of this report, cyclize equally well without such an additive in the presence of a catalytic quantity of iron(III) complexes. Thus a comprehensive series of halo substituted esters were cyclized in excellent yield to the corresponding 4-, 5-, and 6-membered carbocycles. The reaction is extremely mild and selective as demonstrated by experiments wherein alkyl chlorides, acetals, and olefins remain completely intact under the reaction conditions. In addition to introducing a convenient procedure for preparing stereodefined spirocyclic systems, a new ring expansion sequence has been developed that appears extremely general for the preparation of various ring systems.