Organobase-catalyzed Phosphonylation of Alcohols

Dialkyl phosphites are important intermediates for the synthesis of valuable organophosphorus compounds. Catalytic generation of these phosphites without additives under mild conditions is highly desirable. This study presents a novel organobase-catalyzed one-pot synthesis of mixed, symmetric, and cyclic phosphites, utilizing bis(2,2,2-trifluoroethyl) phosphite. Through the activation of alcohols with catalytic amounts of imidazole or 4-dimethylaminopyridine, we improve atom economy, avoid metals, and achieve the first heterogeneously catalyzed phosphonylation of alcohols. Mechanistic investigations, including 1H-NMR, 31P-NMR, HRMS, kinetic, and computational studies, elucidate the reaction pathway.