α-(Z)-(1'-Bromobutylidene)-β-(bromomethyl)-γ-butyrolactone

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: α-(Z)-(1'-Bromobutylidene)-β-(bromomethyl)-γ-butyrolactone
• 英文别名: α-(Z)-(1'-bromobutylidene)-β-bromomethyl-γ-butyrolactone；(3Z)-3-(1-bromobutylidene)-4-(bromomethyl)oxolan-2-one
• 化学式: C₉H₁₂Br₂O₂
• 分子量: 312.001
• InChiKey: ISUGGMOSKODOJO-FPLPWBNLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2-己炔酸 在 Pd₂(dibenzylideneacetone)2*CHCl₃ sodium carbonate 、 lithium bromide 、 copper(ll) bromide 作用下， 以 六甲基磷酰三胺 、 溶剂黄146 为溶剂， 反应 26.0h， 生成 α-(Z)-(1'-Bromobutylidene)-β-(bromomethyl)-γ-butyrolactone
  参考文献：
  名称：

  Palladium-Templated Regio- and Stereoselective Cyclization of 2'-Alkenyl 2-Alkynoates and Its Synthetic Applications

  摘要：

  2'-Alkenyl 2-alkynoates undergo facile stereoselective cyclization to alpha-(haloalkylidene)-gamma-butyrolactones upon treatment with a catalytic amount of palladium complex in the presence of CuX(2) and LiX. When an alkyl group is introduced to the 1'-position of the alkenyl group, unsubstituted 2-propynoates mainly give trans-beta, gamma-disubstituted gamma-lactones, and substituted 2-propynoates afford cis-beta,gamma-disubstituted gamma-lactones. Further elaborations of the halogen atoms and the synthesis of A-factor using this method are exemplified.

  DOI：

  10.1021/jo00110a018

文献信息

• Molecular oxygen promoted oxidative cleavage of carbon-palladium bonds — catalytic cyclization of allylic 2-alkynoates to α-alkylidine-γ-butyrolactones by a PdII complex
  作者：Guoxin Zhu、Xiyan Lu

  DOI：10.1016/0022-328x(95)05781-j

  日期：1996.2

  Molecular oxygen was used as the oxidant to promote the PdII and CuII catalyzed cyclization of acyclic allylic 2-alkynoates, yielding α-haloakylidene-gg-butyrokactones with high stereoselectivity. The stereochemitsyr of halopalladation of the carbon-carbon triple bond, 1,2-induction in the intramolecular carbon-carbon double insertion and oxidative cleavage of carbon-palladium bonds in the cyclization

  分子氧用作氧化剂，以促进Pd II和Cu II催化无环烯丙基2-链烷酸酯的环化反应，产生具有高立体选择性的α-卤代亚烷基-gg-丁酮内酯。详细研究了碳-碳三键的卤代缩合的立体化学，分子内碳-碳双插入的1,2-诱导和环化反应中碳-钯键的氧化裂解。
• Palladium-Templated Regio- and Stereoselective Cyclization of 2'-Alkenyl 2-Alkynoates and Its Synthetic Applications
  作者：Jianguo Ji、Chunming Zhang、Xiyan Lu

  DOI：10.1021/jo00110a018

  日期：1995.3

  2'-Alkenyl 2-alkynoates undergo facile stereoselective cyclization to alpha-(haloalkylidene)-gamma-butyrolactones upon treatment with a catalytic amount of palladium complex in the presence of CuX(2) and LiX. When an alkyl group is introduced to the 1'-position of the alkenyl group, unsubstituted 2-propynoates mainly give trans-beta, gamma-disubstituted gamma-lactones, and substituted 2-propynoates afford cis-beta,gamma-disubstituted gamma-lactones. Further elaborations of the halogen atoms and the synthesis of A-factor using this method are exemplified.