4,4-dicarboethoxy-1,5-heptadiene

• 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: 4,4-dicarboethoxy-1,5-heptadiene
• 化学式: C₁₃H₂₀O₄
• 分子量: 240.299
• InChiKey: GUGHYHWANZLYPS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.25
• 重原子数：
  17.0
• 可旋转键数：
  7.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为产物：
  描述：

  二烯丙基丙二酸二乙酯 在 三乙基硅烷 、 (η(3)-allyl)PdCl * tricyclohexylphosphine 、 四(3,5-二(三氟甲基)苯基)硼酸钠 作用下， 以 二氯甲烷 为溶剂， 生成 3-methyl-4-methylene-cyclopentane-1,1-dicarboxylic acid diethyl ester 、 4,4-dicarboethoxy-1,5-heptadiene
  参考文献：
  名称：

  Development, Synthetic Scope, and Mechanistic Studies of the Palladium-Catalyzed Cycloisomerization of Functionalized 1,6-Dienes in the Presence of Silane

  摘要：

  A 1:1 mixture of the pi-allyl palladium complex (eta (3)-C3H5)Pd(CI)PCy3 Cia) and NaB[3,5-C6H3(CF3)(2)](4) in the presence of HSiEt3 catalyzed the cycloisomerization of diethyl diallylmalonate (2b) to form 4,4-dicarbomethoxy 1,2-dimethylcyclopentane (3b) in 98% yield with 98% isomeric purity. The procedure tolerated a range of functionality including esters, ketones, sulfones, protected alcohols, and substitution at the allylic and terminal olefinic carbon atoms. Cycloisomerization of 2b obeyed zero-order kinetics to >3 half-lives with initial formation of 1,1-dicarboethoxy-4-methyl-3-methylenecyclopentane (4b), followed by secondary isomerization to 3b. Deuterium labeling studies revealed that the conversion of 2b to 4b was accompanied by significant H/D exchange, consistent with an addition/elimination pathway coupled with facile H/D exchange of the Pd-H(D) intermediates with free silane.

  DOI：

  10.1021/ja001730+

文献信息

• Development, Synthetic Scope, and Mechanistic Studies of the Palladium-Catalyzed Cycloisomerization of Functionalized 1,6-Dienes in the Presence of Silane
  作者：Philip Kisanga、Ross A. Widenhoefer

  DOI：10.1021/ja001730+

  日期：2000.10.1

  A 1:1 mixture of the pi-allyl palladium complex (eta (3)-C3H5)Pd(CI)PCy3 Cia) and NaB[3,5-C6H3(CF3)(2)](4) in the presence of HSiEt3 catalyzed the cycloisomerization of diethyl diallylmalonate (2b) to form 4,4-dicarbomethoxy 1,2-dimethylcyclopentane (3b) in 98% yield with 98% isomeric purity. The procedure tolerated a range of functionality including esters, ketones, sulfones, protected alcohols, and substitution at the allylic and terminal olefinic carbon atoms. Cycloisomerization of 2b obeyed zero-order kinetics to >3 half-lives with initial formation of 1,1-dicarboethoxy-4-methyl-3-methylenecyclopentane (4b), followed by secondary isomerization to 3b. Deuterium labeling studies revealed that the conversion of 2b to 4b was accompanied by significant H/D exchange, consistent with an addition/elimination pathway coupled with facile H/D exchange of the Pd-H(D) intermediates with free silane.