Clean inversion of configuration in the Pd-catalyzed cross-coupling of 2-bromo-1,3-dienes

Abstract

The Pd-catalyzed cross-coupling reaction of 2-bromo-1,3-dienes derived from alkyl aldehydes, especially with Cl2Pd(DPEphos) as a catalyst, proceeds with clean stereoinversion of the Br-bearing C=C bond to produce in high yields and in high stereoselectivity (>/=97-98%) conjugated Z,E dienes of potentially high utility in the synthesis of complex natural products. The observed stereoinversion cannot be readily accommodated by the widely accepted pi-sigma-pi rearrangement mechanism for isomerization of ordinary allylpalladium derivatives.