Abstract
In organophosphorus chemistry, several established reactions, such as the conversion of phosphorus trichloride into tertiary phosphines, followed by oxidation and quaternization to form phosphine oxides and phosphonium salts, are widely recognized and routinely applied. In contrast, other potentially valuable transformations, including reverse or complementary versions of these standard synthetic routes, remain largely unexplored or technically challenging. This work introduces two new reaction pathways that broaden the scope of organophosphorus synthesis. The first involves a P-C bond-forming process that enables interconversion of symmetrical phosphine oxides, such as triphenylphosphine oxide (Ph(3)PO), into P-stereogenic phosphine oxides and quaternary phosphonium salts. The second transformation is based on the distinctive reactivity of methoxymethyl (MOM)-substituted quaternary phosphonium salts. These compounds undergo a P-C bond cleavage reaction that results in de-quaternization, allowing the synthesis of mixed-substituent tertiary phosphines from triphenylphosphine as a common precursor. Together, these two processes provide multiple efficient synthetic routes to phosphines, phosphine oxides, and quaternary phosphonium salts. The overall synthetic approach is flexible, so that the target compounds can be obtained through several pathways using different substituent combinations as starting materials.