Asymmetric Kumada-Corriu cross-coupling reaction with Pd2(dba)3 and an N-Ar axially chiral mimetic-type ligand catalyst

A catalyst comprised of Pd-2(dba)(3).CHCl3 and an N-Ar axially chiral mimetic-type ligand, (S)-N-[2-(diphenyl-phosphanyl)naphthalene-1-yl]-2-(piperidinylmethyl)piperidine, provides good enantioselectivities for the asymmetric Kumada-Corriu cross-coupling reaction of 1-phenylethylmagnesium chloride and E-beta-bromostyrene derivatives with which it is more difficult to achieve high enantioselectivity. Furthermore, in the case of styrene derivatives bearing both vinyl and aryl bromide groups, the chemoselective asymmetric cross-coupling reaction of the vinyl bromide group is observed. This N-Ar axially chiral mimetic-type ligand allows easy synthesis of a wide variety of analogues, and starting from the initial ligand, the enantioselectivity of coupling products is improved by modifying the structure in the ligand. (C) 2004 Elsevier Ltd. All rights reserved.