Ruthenium catalysts for carbenoid intramolecular C-H insertion of 2-diazoacetoacetamides and diazomalonic esteir amides

被引：34

作者：

Grohmann, Markus ^{[1
]}

Maas, Gerhard ^{[1
]}

机构：

[1] Univ Ulm, Inst Organ Chem 1, D-89081 Ulm, Germany

来源：

TETRAHEDRON | 2007年 / 63卷 / 49期

关键词：

C-H insertion; diazo compounds; diazoacetoacetamides; lactams; ruthenium;

D O I：

10.1016/j.tet.2007.09.053

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The intramolecular carbenoid C-H insertion of 2-diazoacetoacetamides, leading to gamma- and/or beta-lactams, is catalyzed effectively 2], by dinuclear Ru(I,I) complexes of the type [Ru-2(mu-L-1)(2)(CO)(4)L-2(2)], where L-1 is a bidentate bridging acetate, calix[4]arenedicarboxylate, saccharinate or 6-chloropyridin-2-olate ligand. By comparison with rhodium catalysts, namely dirhodium tetraacetate and dirhodium calix[4]arenedicarboxylate complexes, product yields are similarly high and the regioselectivity of the insertion reaction is the same. Surprisingly, even the ruthenium(0) cluster RU3(CO)(12) was found to be an effective catalyst for carbenoid C-H insertion of 2-diazoacetoacetamides and also of some diazoacetamides. In terms of diastereoselectivity, trans-isomers of beta- and gamma-lactams are obtained. However, the beta-lactam obtained from diazomalonic ester amide 2 yields the cis-isomer stereoselectively, which slowly rearranges to the trans-isomer. (c) 2007 Elsevier Ltd. All rights reserved.

引用

页码：12172 / 12178

页数：7

共 38 条

[1] Diruthenium(I,I) saccharinate complexes: Synthesis, molecular structure, and evaluation as catalysts for carbenoid reactions of diazoacetates [J].