Rhodium-Catalyzed Enantioselective Radical Addition of CX4 Reagents to Olefins

被引：67

作者：

Chen, Bo ^{[1
]}

Fang, Cheng ^{[2
,3
]}

Liu, Peng ^{[2
]}

Ready, Joseph M. ^{[1
]}

机构：

[1] UT Southwestern Med Ctr, Dept Biochem, 5323 Harry Hines Blvd, Dallas, TX 75390 USA

[2] Univ Pittsburgh, Dept Chem, Pittsburgh, PA 15260 USA

[3] Univ Pittsburgh, Computat Modeling & Simulat Program, Pittsburgh, PA 15260 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2017年 / 56卷 / 30期

关键词：

alkenes; asymmetric catalysis; enantioselectivity; radical reactions; rhodium; ACTIVATED PHOTOREDOX CATALYSIS; SECONDARY ALKYL ELECTROPHILES; LEWIS-ACID CATALYSIS; VISIBLE-LIGHT; OXIDATIVE ADDITION; CROSS-COUPLINGS; ASYMMETRIC ADDITION; METHYL-IODIDE; ALKENES; COMPLEX;

D O I：

10.1002/anie.201704074

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We describe the synthetically useful enantioselective addition of Br-CX3 (X = Cl or Br) to terminal olefins to introduce a trihalomethyl group and generate optically active secondary bromides. Computational and experimental evidence supports an asymmetric atom-transfer radical addition (ATRA) mechanism in which the stereodetermining step involves outer-sphere bromine abstraction from a [(bisphosphine)(RhBrCl)-Br-II] complex by a benzylic radical intermediate. This mechanism appears unprecedented in asymmetric catalysis.

引用

页码：8780 / 8784

页数：5

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