Asymmetric alkylation is a fundamental strategy for the stereoselective construction of chiral molecules, traditionally focusing on control over the carbon stereocenters. Recent advances have extended this approach to heteroatom-centered systems, enabling selective C−heteroatom bond formation to generate heteroatom stereogenicity. While sulfur-based alkylations have attracted considerable attention in recent studies, efcient alkylation strategies for the synthesis of P-stereogenic compounds remain limited despite their pivotal signifcance in catalysis and drug development. Here, we present an organocatalytic enantioselective methylation of prochiral phosphinic acids to access P(V)-stereogenic phosphorus compounds. Employing a cinchonidine-derived phase-transfer catalyst, the formation of a tight ion pair with a prochiral phosphinic acid anion enables highly stereoselective formation of an O−C bond using simple methylating agents under mild conditions. The resulting chiral phosphinates serve as linchpin intermediates that can undergo stereospecifc nucleophilic substitution to afford a broad range of P-stereogenic molecules, including tertiary phosphine oxides, phosphinamides, and phosphinates. These chiral phosphorus compounds display promising biological activities, underscoring their potential in the development of agrochemical agents.

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