Halophosphoryloxylation of Alkenes via Cooperative Activation between a Lewis Base and a Silyl-Based Lewis Acid

Abstract A new strategy for the catalytic halophosphoryloxylation of alkenes via the cooperative activation between a Lewis base and a silyl-based Lewis acid has been developed. The N-silylation of allyl phosphoramidates enabled an unprecedented halocyclization, furnishing the desired 1,2-halophosphoryloxylated compounds in high yield. Several control experiments indicated that the interaction between the silyl group and chloride ion plays an important role in determining both the reactivity and the chemoselectivity of the reaction.