Upon treatment with LDA or alkyllithium, enantiomers of P-chiral phosphinates, phosphinothioates, phosphinoamidates, thionophosphinates, thionophosphinothioates and thionophosphinoamidates undergo clean [1,3]- and [1,2]-rearrangements with complete stereoselectivity, with retention of configuration at phosphorus, to provide functionalised tertiary phosphine oxides and phosphine sulfides; the [1,2]-rearrangements of the phosphinoamidates are previously unrecorded.