Origins of enantioselectivity in reductions of ketones on cinchona alkaloid modified platinum

被引：91

作者：

Vayner, G

Houk, KN

Sun, YK

机构：

[1] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA

[2] Merck & Co Inc, Rahway, NJ 07065 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2004年 / 126卷 / 01期

关键词：

D O I：

10.1021/ja035147f

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A model to explain the stereoselectivities of reductions of activated ketones on cinchona alkaloid modified platinum is proposed and is supported by calculations by density functional and force field methods. The model involves nucleophilic catalysis by the cinchona alkaloid. The zwitterionic adduct between a cinchona alkaloid and ketone is adsorbed on Pt through the quinoline ring and two heteroatoms and is subsequently reduced with inversion. The model rationalizes the observed stereoselectivities for hydrogenation of carbonyl compounds.

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页码：199 / 203

页数：5

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