Abstract The reaction of (+)-(i-PrO) MeP (O) SMe with phenylmagnesium bromide in tetrahydrofuran affords (+)-(i-PrO) MeP (O) Ph, representing the first example of a stereospecific synthesis of a phosphinate ester from a phosphonothiolate ester. Levorotatory (MeS) MeP (O) Ph is converted into (R)-(+)-n-PrMeP (O) Ph with inversion of configuration by reaction with n-propylmagnesium bromide. The two Grignard reactions are correlated ...