Recent Advances in Organophosphorus-Catalyzed Borylation and Silylation Reactions

Over the past few decades, organophosphorus catalysis has emerged as a robust platform for the preparation of highly functionalized molecules with excellent control of reactivity and selectivity. Organophosphorus catalysis has the advantages of mild and metal-free reaction conditions. The easy-to-tune electronic and steric properties of phosphorus provide an easy handle for developing efficient synthetic methodologies with high stereochemical fidelity. This review describes the efforts to introduce boron and silicon functionalities into organic substrates catalyzed by organophosphorus compounds. These catalysts are categorized into nucleophilic, electrophilic, and biphilic phosphorus catalysts. Phosphorus compounds efficiently catalyze hydroboration of various unsaturated systems, carbonyl compounds, imines, etc.; hydro-/cyano-silylation of carbonyls; and silylation of alcohols. The present review emphasizes the scope of nucleophilic, electrophilic, and biphilic phosphorus-based catalysis to introduce boron and silicon functionalities into organic compounds, mainly from the recent decade.