Tandem Regio- and Stereoselective Organocuprate-Mediated Bis-Allylic Substitutions

Abstract

anti-5-Acetoxy-4-halo-alpha,beta-enoates undergo sequential or tandem reactions with two different magnesium cuprate reagents to afford anti-2,3-dialkyl-4,5-enoates in high chemical yield and with excellent diastereoselectivity. The one-pot tandem procedure can be achieved with 30 mol % of CuCN and affords a rapid stereoselective combinatorial approach to vicinal disubstituted gamma,delta-enoates containing functionality at either end of the carbon chain for subsequent functional group elaboration. The methodology should provide a powerful practical strategy for acyclic stereoselection.