(CHELATING DIPHOSPHINE)RHODIUM-CATALYZED DEUTERIOFORMYLATION OF 1-HEXENE - CONTROL OF REGIOCHEMISTRY BY THE KINETIC RATIO OF ALKYLRHODIUM SPECIES FORMED BY HYDRIDE ADDITION TO COMPLEXED ALKENE

被引：119

作者：

CASEY, CP

PETROVICH, LM

机构：

[1] Department of Chemistry, University of Wisconsin, Madison

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1995年 / 117卷 / 22期

关键词：

D O I：

10.1021/ja00127a014

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The deuterioformylation of 1-hexene catalyzed by (chelating diphosphine)rhodium catalysts gave nearly exclusive formation of CH3(CH2)(3)CHDCH2CDO and CH3(CH2)(3)CH(CH2D)CDO, with the deuterium label at the beta-carbon and at the aldehyde carbon. Very little deuterium was incorporated into recovered hexenes. These results establish that the regiochemistry of aldehyde formation is set by a largely irreversible addition of a rhodium hydride to complexed 1-hexene to produce an alkylrhodium intermediate that is committed to aldehyde formation. Plausible steric explanations for the increased n:i aldehyde regioselectivity seen for diequatorial chelates compared with apical-equatorial chelates are considered. However, such steric explanations are not supported by molecular mechanics calculations of probable transition states.

引用

页码：6007 / 6014

页数：8