Synthesis of P-stereogenic phosphonothioates via alcoholysis of phosphonothioates with a binaphthyl group

The reaction of phosphonothioates having a binaphthyl group with alkoxides proceeded via transfer of the axial chirality of the binaphthyl group to the central chirality of the phosphorus atom to give P-stereogenic phosphonothioates with moderate-to-excellent diastereoselectivities. The reaction of phosphonoselenoates also proceeded in a similar fashion. The selenium atom of the obtained product could be excluded with tributylphosphine to give a trivalent phosphonite, which was isolated as a boron complex.