This chapter describes recent advances in metal-catalyzed C–P bond formation, which may be classified into two types of reactions. In hydrophosphination and related processes, P–H groups add across unsaturated C–X (X = C, N, O) bonds. Phosphination of electrophiles typically results in substitution at sp2 or sp3 carbon; the P–H group is removed, often by a base. The scope of both nucleophilic and electrophilic partners in these processes is surveyed, and the proposed mechanisms and intermediates in the metal-catalyzed reactions are described.
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