TRANSITION METHAL-CATALYZED SUBSTITUTION REACTION OF ALLYLIC PHOSPHATES WITH GRIGNARD REAGENTS

Article abstract of DOI:10.1016/S0040-4020(01)90454-5

S_N2-selective Grignard coupling with primary allylic diphenylphosphates was successfully achieved using Ni or Fe catalyst.In sharp contrast, a catalytic amount of CuCN*2LiCl promoted a S_N2'-selective coupling reaction.In the presence of the copper catalyst, stereochemically homogeneous γ-disubstituted allyl Grignard reagents reacted at the less substituted allylic terminus (α-position) with an allylic diphenylphosphate selectively without losing the double bond geometry.