Chiral dirhodium(II) catalysts with orthometalated aryl phosphine ligands:: Synthesis and application for enantioselective C-H insertion of α-diazo ketones

被引：62

作者：

Estevan, F

Herbst, K

Lahuerta, P

Barberis, M

Pérez-Prieto, J

机构：

[1] Univ Valencia, Dept Quim Inorgan, Fac Quim, E-46100 Valencia, Spain

[2] Univ Valencia, Fac Farm, Dept Quim Organ, Inst Ciencia Mol, E-46100 Valencia, Spain

来源：

ORGANOMETALLICS | 2001年 / 20卷 / 05期

关键词：

D O I：

10.1021/om0010060

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Racemic dirhodium(II) complexes derived from orthometalated aryl phosphines, Rh-2(O2CCH3)(2)(pc)(2) (pc = orthometalated phosphine, with head-to-tail arrangement) (1-7), are isolated as pure enantiomers by conventional resolution methods. They are the first examples of dirhodium(II) chiral catalysts without chiral ligands. These compounds have been used in the cyclization of ol-diazo ketones; the influence of catalyst and substrate on enantioselectivity is studied. Results are compared with those obtained for reactions catalyzed by Rh-2(protos)(4) and Rh-2(protos)(2)(pc)(2) [ProtosH (8) = N-(4-methylphenylsulfonyl-L-proline)] (9-22). Only catalysts 1-7 afford a high level of enantioselectivity in the synthesis of carbocycles from alpha -diazo ketones.

引用

页码：950 / 957

页数：8

共 44 条

[1] Highly enantioselective construction of the key azetidin-2-ones for the synthesis of carbapenem antibiotics via intramolecular C-H insertion reactions of α-methoxycarbonyl-α-diazoacetamides catalysed by chiral dirhodium(II) carboxylates [J].