Mechanism of Nakamura's Bisphosphine-Iron-Catalyzed Asymmetric C(sp2)-C(sp3) Cross-Coupling Reaction: The Role of Spin in Controlling Arylation Pathways

被引：59
|
作者：
Lee, Wes [1 ]
Zhou, Jun [1 ]
Gutierrez, Osvaldo [1 ]
机构：
[1] Univ Maryland, Dept Chem & Biochem, College Pk, MD 20742 USA
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2017年 / 139卷 / 45期
关键词：
DENSITY-FUNCTIONAL THEORY; ARYL-GRIGNARD-REAGENTS; ALKYL-HALIDES; ALKENYL HALIDES; KUMADA; THERMOCHEMISTRY; NUCLEOPHILES; DERIVATIVES; COMPLEX; FERRATE;
D O I：
10.1021/jacs.7b06377
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Quantum mechanical calculations are employed to investigate the mechanism and origin of stereoinduction in asymmetric iron-catalyzed C(sp(2))-C(sp(3)) cross-coupling reaction between Grignard reagents and alpha-chloroesters. A coherent mechanistic picture of this transformation is revealed. These results have broad implications for understanding the mechanisms of iron-catalyzed cross-coupling reactions and rational design of novel iron-based catalysts for asymmetric transformations.
引用
收藏
页码：16126 / 16133
页数：8
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