P-stereogenic phosphinothioic acids, phosphonothioic acids and their esters: Syntheses, reactions, and applications

Abstract Since the first synthesis of an optically active phosphonothioic acid in 1956, the P S bonds containing P-stereogenic phosphinothioic and phosphonothioic acids have received attention for their unique reactivity and biological activity compared to their P O analogues. In this review, we first summarize their common syntheses and examine the strategies that allow access to their enantiomerically pure forms. Next, we discuss their reactivity toward a variety of reactants at the three potential reactive sites, i.e., oxygen, sulfur, and phosphorus atoms. Finally, we detail the application of P-stereogenic phosphinothioic and phosphonothioic acids as organocatalysis and chiral discriminating agents.