Synthesis of chiral ortho-thio-substituted phenyl phosphonodiamidates via a P–S to P–C rearrangement

Abstract The ortho -lithiation of a phenyl phosphorodiamidothioate derived from an enantiopure C 2 -symmetric diamine is studied. It is shown that the migration of the diaminophosphoryl group from sulfur to carbon, leading to an ortho -sulfanylated phenyl phosphonodiamidate, only occurs in the presence of an alkylating agent or a Lewis acid as BF 3 ·Et 2 O. The influence of the chiral diaminophosphoryl group on the stereoselectivity of the oxidation of the ortho -sulfanyl or alkylsulfanyl group is also examined.