Mechanistic Insights into Copper-Catalyzed Michael Reactions

被引：5

作者：

Perez, Elisabet ^{[1
,2
]}

Moreno-Manas, Marcial ^{[1
]}

Maria Sebastian, Rosa ^{[1
]}

Vallribera, Adelina ^{[1
]}

Jutand, Anny ^{[2
]}

机构：

[1] Univ Autonoma Barcelona, Dept Chem, E-08193 Barcelona, Spain

[2] Ecole Normale Super, Dept Chim, CNRS, UPMC,UMR 8640, F-75231 Paris 5, France

来源：

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2010年 / 07期

关键词：

Copper; Michael addition; Reaction mechanisms; QUATERNARY STEREOCENTERS; DIRECT AMINATION; BETA-KETOESTERS; ADDITIONS; CONSTRUCTION;

D O I：

10.1002/ejic.200900985

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The mechanism of the Michael reaction between 2-(ethoxycarbonyl)cyclopentanone (2) and methyl vinyl ketone (3) catalyzed by the copper(II) salt [Cu(5-tBu-Sal)(2)] (1) has been investigated in toluene. The kinetics of the reaction of the catalyst I with the oxo ester 2 has been investigated by UV/Vis spectroscopy. It has been established that [Cu(5-tBu-Sal)(2)] (1) reacts with 2 in a first-order reaction, which is retarded by 5-tBu-Sal-H (6), formed in the reaction after the reversible dissociation of [Cu(5-tBu-Sal)(2)] to [Cu(5-tBu-Sal)](+) and 5-tBu-Sal(-) and the subsequent reversible deprotonation of 2 by 5-tBu-Sal(-). The formation of the mixed complex [Cu(5-tBu-Sal)(enolate-2)] (5) is proposed and has been characterized by cyclic voltammetry. The rate constant for the overall reaction leading to [Cu(5-tBu-Sal)(enolate-2)] (5) has been determined. The reaction of the mixed complex 5 with methyl vinyl ketone (3), investigated by cyclic voltammetry, is proposed as the rate-determining step.

引用

页码：1013 / 1019

页数：7

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