The reaction of organocuprate reagents R'2Cu(CN)Li2.BF3 with gamma-bromo conjugated N-acyl sultams derived from camphor gave, with high regio- and stereoselectivity, compounds arising from a SN' allylic substitution. Reductive removal of the chiral auxiliary furnished alpha-substituted beta, gamma-unsaturated alcohols of excellent enantiomeric purity.