Rhodium-mediated intramolecular C-H insertion: Probing the geometry of the transition state

被引：41

作者：

Taber, DF ^{[1
]}

Malcolm, SC ^{[1
]}

机构：

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

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1998年 / 63卷 / 11期

关键词：

D O I：

10.1021/jo9803434

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The unsymmetrical alpha-diazo ester 1b, derived from the chiral naphthylborneol 5, was cyclized with a set of rhodium carboxylates (L = CF3CO2, CH3CO2, CH3(CH2)(6)CO2, (CH3)(3)CCO2). The ratio of the three major products ((R,R)-3b, (S,S)-3b, 4b) was determined. It was found that the rhodium catalyst derived from pivalic acid gave the highest ratio of 3b:4b. Lowering the temperature of the reaction (L = (CH3)(3)CCO2) increased both the yield and the diastereoselectivity of the cyclization. From these results and from our computational analysis, it is concluded that the ester carbonyl and the rhodium carbenoid are probably syn in the transition state leading to cyclization.

引用

页码：3717 / 3721

页数：5

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