Rh(I)-Catalyzed Intermolecular Hydroacylation: Enantioselective Cross-Coupling of Aldehydes and Ketoamides

被引：51

作者：

Kou, Kevin G. M. ^{[1
,2
]}

Le, Diane N. ^{[1
]}

Dong, Vy M. ^{[1
]}

机构：

[1] Univ Calif Irvine, Dept Chem, Irvine, CA 92697 USA

[2] Univ Toronto, Dept Chem, Toronto, ON M5S 3H6, Canada

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2014年 / 136卷 / 26期

基金：

美国国家卫生研究院;

关键词：

ALPHA-KETO AMIDE; INTRAMOLECULAR HYDROACYLATION; STEREOSELECTIVE REDUCTION; HOMOGENEOUS CATALYSIS; TISHCHENKO REACTION; ASYMMETRIC HYDROGENATION; OXIDATION LEVEL; ATOM ECONOMY; CONVERSION; COMPLEXES;

D O I：

10.1021/ja504296x

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Under Rh(I) catalysis, alpha-ketoamides undergo intermolecular hydroacylation with aliphatic aldehydes. A newly designed Josiphos ligand enables access to alpha-acyloxyamides with high atom-economy and enantioselectivity. On the basis of mechanistic and kinetic studies, we propose a pathway in which rhodium plays a dual role in activating the aldehyde for cross-coupling. A stereochemical model is provided to rationalize the sense of enantioinduction observed.

引用

页码：9471 / 9476

页数：6