Collect. Czech. Chem. Commun.
2007, 72, 1107-1121
https://doi.org/10.1135/cccc20071107
In Search of New Approaches to Asymmetric Conjugate Addition: Screening Studies on the Use of [Zn(bpy*)X(R)] Reagents and α,β-Unsaturated Amide Michael Acceptors
Alexander J. Blake, Daniela Giunta, Jonathan Shannon, Maurizio Solinas, Francesca Walzer and Simon Woodward*
School of Chemistry, The University of Nottingham, University Park, Nottingham NG7 2RD, United Kingdom
Abstract
Conjugate additions of [Zn(bpy*)Cl(Et)] (bpy* = 4,4'-di-tert-butyl-2,2'-bipyridine) to cyclohex-2-en-1-one are promoted by ZnMe2 in 88% ee but in moderate yield under CuI phosphoramidite catalysis. In the absence of ZnMe2 the [Zn(bpy*)Cl(Et)] is inactive indicating a Schlenk-type equilibrium. Other derivatives of [Zn(bpy*)Cl(R)] (R = Bu, 4-methylbenzyl), prepared in situ from [ZnCl(R)] and the bipyridine give low yields due to competing chloride abstraction. 13C NMR studies indicate facile organo-ligand exchange between [Zn(bpy*)(Et)2] and [Zn(bpy*)Cl2] complexes. In the presence of the bipyridine, [ZnBr(allyl)] disproportionates into [Zn(bpy*)Br2] and [Zn(bpy*)(allyl)2] species. In separate studies, simple (E)-MeCH=CHCONMeR (R = Me, OMe) α,β-unsaturated amides undergo asymmetric 1,4-addition of EtMgBr in 75-99% yield and 48-79% ee in the presence of the diphosphines JosiPhos or MeDuPhos and copper(I) sources.
Keywords: Bipyridyl complexes; Zinc; Enamides; Copper catalysis; Grignard reagents; Asymmetric conjugate additions; 1,4-Additions; Phosphoramidite ligands; X-Ray diffraction.
References: 47 live references.
