This review presents the use of cyclic tri- and pentavalent amidoesters and diamides with a stereogenic phosphorus as chiral stoichiometric auxiliaries in asymmetric synthesis. It shows that these compounds are especially useful for the preparation of selected acyclic enantiomerically (diastereomerically) pure (or enriched) tricoordinated-trivalent and tetracoordinated-pentavalent derivatives and as precursors of stereogenic phosphorus-containing carbanions. Their utility in a few other asymmetric reactions is also discussed.