Cyclopentane construction by Rh-catalyzed intramolecular C-H insertion: Relative reactivity of a range of catalysts

被引：43

作者：

Taber, DF ^{[1
]}

Joshi, PV ^{[1
]}

机构：

[1] Univ Delaware, Dept Chem & Biochem, Newark, DE 19716 USA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2004年 / 69卷 / 12期

关键词：

D O I：

10.1021/jo0303766

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The preparation and Rh-mediated cyclization of the alpha-diazoester 1 are outlined, and its utility in determining the elements that contribute to the reactivity of the intermediate Rh-carbenoid is presented. The rate of disappearance of diazo ester 1 catalyzed by several representative Rh(II) complexes was determined. The observed relative rate constants for the reaction of the Rh(II) complexes with 1 varied over a range of >10(7). The reactivity of the Rh-carbenoid intermediate was explored using the ratio of the sum of (3 + 4 + 5) to 2 (cyclization vs elimination), the ratio of 3 to the sum of (4 + 5) (chemo selectivity), and the ratio of 4 to 5 (diastereoselectivity). It is striking that these four measures of reactivity were found to be independent of each other.

引用

页码：4276 / 4278

页数：3

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