Understanding Rate Acceleration and Stereoinduction of an Asymmetric Giese Reaction Mediated by a Chiral Rhodium Catalyst

被引：42

作者：

Tutkowski, Brandon ^{[1
]}

Meggers, Eric ^{[2
]}

Wiest, Olaf ^{[1
,3
]}

机构：

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

[2] Philipps Univ Marburg, Fachbereich Chem, Hans Meerwein Str 4, D-35043 Marburg, Germany

[3] Peking Univ, Sch Chem Biol & Biotechnol, Shenzhen Grad Sch, Lab Computat Chem & Drug Design, Shenzhen 518055, Peoples R China

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2017年 / 139卷 / 24期

基金：

美国国家科学基金会;

关键词：

LEWIS-ACID CATALYSIS; PHOTOREDOX CATALYSIS; RADICAL ADDITIONS; CONJUGATE ADDITIONS; BENZYL RADICALS; LIGHT; STATES; REGIOSELECTIVITY; SELECTIVITY; MECHANISM;

D O I：

10.1021/jacs.7b01786

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The surprising acceleration of the addition of electron-rich radicals to alpha,beta-unsaturated 2-acyl imidazoles by a chiral-at-metal rhodium catalyst is investigated. M06/Lanl2DZ (Rh),6-31G(d) calculations reproduce the observed rate acceleration and shed light on a catalyst design where a rigid chiral pocket with a steric interaction >5 angstrom from the chiral metal center leads to the observed high stereoinduction. Analysis of the molecular orbitals of two key addition transition states emphasize the role of the catalyst as a Lewis acid without significant charge transfer.

引用

页码：8062 / 8065

页数：4

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