SYNTHESIS OF CYCLOPROP[C]INDOL-5-ONES FROM 4-DIAZO-3-[N-(2-PROPENYL)AMIDO]CYCLOHEXADIEN-1-ONES - EXPLORATION OF COPPER(I) AND COPPER(II) COMPLEXES AS CATALYSTS

被引：69

作者：

SUNDBERG, RJ

PITTS, WJ

机构：

[1] Department of Chemistry, University of Virginia, Charlottesville, Virginia 22901, McCormick Road

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1991年 / 56卷 / 09期

关键词：

D O I：

10.1021/jo00009a023

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The cyclization of 4-diazo-3-[N-(2-propenyl)amido]cyclohexadienones to cycloprop[c]indol-5-ones under the influence of copper(I) and copper(II) compounds has been investigated. Catalysis is observed with copper(I) triflate, the carbon monoxide complex of copper(I) triflate, and the carbon monoxide complexes of trifluoropentanedionato- and hexafluoropentanedionatocopper(I). The best results, essentially quantitative conversion, are achieved with a catalyst solution containing trifluoropentanedionatocopper(I) carbonyl and 1 equiv of n-butylamine. No significant enantioselectivity is observed with a chiral salicyliminatocopper(II), [(trifluoroacetyl)camphorato]copper(I) carbonyl, or a trifluoropentanedionatocopper(I) carbonyl solution containing (S)-alpha-naphthylethylamine. A mechanistic interpretation involving reductive dediazonization, exo-trig radical cyclization, and cyclopropane formation by the resulting intermediate is proposed.

引用

页码：3048 / 3054

页数：7

共 34 条

[1] INTRAMOLECULAR ALKENE ARYLATIONS FOR RAPID ASSEMBLY OF POLYCYCLIC SYSTEMS CONTAINING QUATERNARY CENTERS - A NEW SYNTHESIS OF SPIROOXINDOLES AND OTHER FUSED AND BRIDGED RING-SYSTEMS [J].