On the mechanism of the rhodium catalyzed acrylamide hydrogenation

被引：8

作者：

Verdolino, Vincenzo ^{[1
]}

Forbes, Aaron ^{[1
]}

Helquist, Paul ^{[1
]}

Norrby, Per-Ola ^{[2
]}

Wiest, Olaf ^{[1
]}

机构：

[1] Univ Notre Dame, Dept Chem & Biochem, Notre Dame, IN 46556 USA

[2] Univ Gothenburg, Dept Chem, SE-41296 Gothenburg, Sweden

来源：

JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL | 2010年 / 324卷 / 1-2期

基金：

美国国家科学基金会;

关键词：

Hydrogenation; Mechanism; Electronic structure; Rhodium; EFFECTIVE CORE POTENTIALS; MOLECULAR CALCULATIONS; ASYMMETRIC HYDROGENATION; DIPHOSPHINE LIGANDS; REACTION PATHWAYS; ENANTIOSELECTIVITY; REDUCTION; ENAMIDES; COMPLEX; ORIGIN;

D O I：

10.1016/j.molcata.2010.02.026

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The hydrogenation of acrylamides using chiral Rh(I) complexes is an attractive method for the enantioselective synthesis of highly functionalized intermediates. It has been employed less frequently than the related Rh(I) catalyzed hydrogenation of enamides and the mechanism of the reaction is not well understood. The parent reaction of acrylamide with a simple Rh(I) bisphosphine complex was studied at the B3LYP/LanL2TZ(f)/6-31++G** level of theory and shows a number of interesting differences compared to the mechanism of the enamide reaction. The minimum energy reaction pathway was found to involve attack of the molecular hydrogen parallel to the C-Rh-P bond, followed by an isomerization at the stage of the dihydride complex to give an altered orientation of the hydride, which is then transferred to the beta-carbon. (C) 2010 Elsevier B.V. All rights reserved.

引用

页码：9 / 14

页数：6

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