A kinetic study on the pairwise competition reaction of α-diazo esters with rhodium(II) catalysts:: Implication for the mechanism of Rh(II)-carbene transfer

被引：53

作者：

Qu, ZH ^{[1
]}

Shi, WF ^{[1
]}

Wang, JB ^{[1
]}

机构：

[1] Peking Univ, Coll Chem, Dept Biol Chem, Minist Educ,Key Lab Bioorgan Chem & Mol Engn, Beijing 100871, Peoples R China

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2001年 / 66卷 / 24期

关键词：

D O I：

10.1021/jo0107352

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The relative rate constants for the Rh(II)-mediated diazo decomposition of a series of para- or meta-substituted diazophenylacetates were measured through intermolecular competition. The kinetic data were further subjected to Hammett correlation analysis and were found to have better linear correlation with sigma (+). Reaction constants for four Rh(II) catalysts have been obtained, Rh-2(OAc)(4) (rho = -1.29 with sigma (+), r = -0.99), Rh-2(Ooct)(4) (rho = -1.31 with sigma (+), r = -0.99), Rh-2(acam)(4) (rho = -1.18 with sigma (+), r = -0.99), Rh-2(O2CCF3)(4) (rho = -1.46 with sigma (+), r = -0.99). The mechanistic implications of these data are discussed.

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页码：8139 / 8144

页数：6

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