Homogeneous and Heterogeneous Pd-Catalyzed Selective C–P Activation and Transfer Hydrogenation for “Group-Substitution” Synthesis of Trivalent Phosphines

A "group-substitution" synthesis of trivalent phosphines via a C-P activation of phosphonium salts is reported. The alkyl groups were introduced by alkylation of phosphines to form phosphonium salts. The "de-arylation" of phosphonium salts was achieved by C-P activation and transfer hydrogenation with homogeneous or heterogeneous Pd (0) catalysts. With this method, a series of trivalent phosphines were prepared from commercially available triarylphosphines. A chiral monophosphine ligand could be prepared from BINAP in a "de-phosphination" process.