ENANTIOSELECTIVITY AND CIS/TRANS-SELECTIVITY IN DIRHODIUM(II)-CATALYZED ADDITION OF DIAZOACETATES TO OLEFINS

被引：41

作者：

MULLER, P ^{[1
]}

BAUD, C ^{[1
]}

ENE, D ^{[1
]}

MOTALLEBI, S ^{[1
]}

DOYLE, MP ^{[1
]}

BRANDES, BD ^{[1
]}

DYATKIN, AB ^{[1
]}

SEE, MM ^{[1
]}

机构：

[1] TRINITY UNIV,DEPT CHEM,SAN ANTONIO,TX 78212

来源：

HELVETICA CHIMICA ACTA | 1995年 / 78卷 / 02期

关键词：

D O I：

10.1002/hlca.19950780217

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The Rh-II-catalyzed carbenoid addition of diazoacetates to olefins was investigated with [Rh-2{(4S)-phox}(4)] (1; phox = tetrakis[(4S)-tetrahydro-4-phenyloxazol-2-one]} [Rh-2{(2S)-mepy)(4)] (2; mepy = tetrakis[methyl (2S)tetrahydro-5-oxopyrrole-2-carboxylate]), and [Rh-2(OAc)(4)] (3). While catalysis with 2 and 3 afford preferentially trans-cyclopropanecarboxylates, the cis-isomers are the major products with 1. In general, the enantioselectivities achieved with 1 and 2 are comparable. Additions catalyzed by 1 are strongly sensitive to steric effects. Highly substituted olefins afford cyclopropanes in only poor yield. The preferential cis-selectivity observed in reactions catalyzed by 1 is attributed to dominant interactions between the ligand of the catalyst and the sbustituents of both olefin and diazoacetate, which overrule the steric interactions between olefin and diazoacetate in the transition slate for carbene transfer.

引用

页码：459 / 470

页数：12

共 55 条

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