Achieving Organocatalytic Control of P(III)-Centered Chirality for the Construction of P(III)/(V) Stereogenic Compounds.

P(III)/(V)-chiral compounds are indispensable motifs in asymmetric catalysis, pharmaceuticals, and agrochemicals, yet their catalytic asymmetric synthesis remains intrinsically challenging. Although transition-metal catalysis has enabled major advances via nucleophilic P(III) intermediates, organocatalytic strategies that directly activate trivalent phosphorus as an electrophile remain largely unexplored. Herein, we report an organocatalytic asymmetric platform for the construction of P(III)-stereogenic phosphinites through direct nucleophilic substitution of readily available chlorophosphines with phenols and alcohols. Central to this strategy is a chiral isothiourea catalyst that engages the trivalent phosphorus center to generate a key chiral P-catalyst intermediate, enabling catalyst-controlled P-O bond formation in high selectivity. Density functional theory calculations reveal that mild chloride-assisted pyramidal inversion of the phosphorus center enables an efficient dynamic kinetic resolution process. This method provides broad access to enantioenriched P(III) phosphinites, which can be readily diversified via postsynthetic transformations to furnish structurally diverse P(III) and P(V) chiral frameworks, including chiral metal-phosphine complexes. The resulting compounds exhibit promising antimicrobial activity against representative plant pathogens, highlighting the potential of this organocatalytic strategy for phosphorus-based agrochemical development.