Completely stereoselective PC bond formation via base-induced [1,3]- and [1,2]-intramolecular rearrangements of aryl phosphinates, phosphinoamidates and related compounds: generation of P-chiral β-hydroxy, β-mercapto- and α-amino tertiary phosphine oxide

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.