Nickel and Palladium-Catalyzed Cross-Couplings that Form Carbon-Heteroatom and Carbon-Element Bonds

The transition-metal catalyzed addition of heteroatom nucleophiles to aryl and vinyl halides is reviewed. This chemistry typically involves a nickel- or palladium-based catalyst containing phosphine ligands. In recently developed palladium-catalyzed chemistry, aryl halides react with amines in the presence of base to form arylamines. In similar chemistry cataly­zed by both nickel and palladium, aryl and vinyl halides react with alkali metal or tin thiolates or selenides to form aryl and vinyl sulfides, while the reaction of different phosphorus compounds, such as phosphides, phosphonates, and phosphonites, with aryl halides gives compounds with new aryl-p· linkages. In addition to these typically nucleophilic heteroatoms, electrophilic heteroatoms such as boron, silicon, tin, and germanium have also been coupled to aryl electrophiles. The review closes with a brief summary of the general reaction pathways of these C-X bond-forming processes.