Stereochemistry of imine reduction by a hydroxycyclopentadienyl ruthenium hydride

被引：55

作者：

Casey, CP ^{[1
]}

Bikzhanova, GA ^{[1
]}

Guzei, IA ^{[1
]}

机构：

[1] Univ Wisconsin, Dept Chem, Madison, WI 53706 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2006年 / 128卷 / 07期

关键词：

D O I：

10.1021/ja056402u

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The stereochemistry of hydrogen transfer from [2,5-Ph-2-3,4-Tol(2)(eta(5)-C4COD)]Ru(CO)(2)D to N-aryl imines to give amine complexes was shown to be mostly trans stereospecific. Stereospecific hydrogen transfer is proposed to generate an amine and a coordinatively unsaturated ruthenium intermediate in close proximity. Coordination of the amine is proposed to occur faster than lone pair inversion of the amine. In contrast, hydrogen transfer to N-alkyl imines is stereorandom. It is proposed that stereochemistry is lost in part due to the reversibility of the hydrogen transfer being faster than amine coordination.

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页码：2286 / 2293

页数：8

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