Catalytic construction of P-stereogenic centers

P-Stereogenic organophosphorus compounds are important in asymmetric catalysis, medicinal chemistry and functional-molecule synthesis, however catalytic control of configuration at phosphorus remains challenging because reactivity and configurational stability vary markedly across P(III) and P(V) systems. This Review surveys catalytic methods developed mainly over the past decade and classifies them according to the location of the enantiodetermining event. Direct approaches include asymmetric P-C and P-heteroatom bond formation, catalytic access to P(III)-stereogenic phosphines, C-P bond reorganisation and oxidation-state editing, whereas indirect approaches establish P stereogenicity through enantioselective differentiation of P-bound substituents by C-H functionalisation, cyclisation, cascade reactions and substituent-level desymmetrisation. Particular attention is given to recent P(V) substitution chemistry and open-shell processes involving P-centered radicals and radical ions. Applications in chiral ligands, ProTides, stereodefined oligonucleotides and chiroptical molecules are discussed together with remaining challenges in enantioconvergence, configurational stability, oxidation-state interconversion and stereospecific downstream functionalisation.