Organometallics Using Organosulfur Compounds: Exchange of Information between Catalytic and Stoichiometric Reactions

The utility of transition metal-catalyzed reactions with organic sulfur compounds, which have been known to act as a "catalyst poison", has not been well-studied until recently. However, ever since the Pd-catalyzed cis-addition of diaryl disulfides to terminal alkynes was reported in 1991, a variety of regio- and stereoselective metal-catalyzed addition reactions of the compounds with S-G bonds (G; element or group) to unsaturated compounds have been developed. We herein review our achievements: (1) Pd-catalyzed addition of diaryl disulfide to isocyanide, (2) Pd-catalyzed reactions with sulfenamides, carbon monoxide, and terminal alkynes, (3) oxidative additions of S-C bonds of vinyl sulfides and thioesters to Pt(0)-complex and the application to a series of carbothiolations and a unique one-pot cyclization, (4) thermal and photo-promoted insertions of terminal and internal alkynes into S-M (M = Pd, Pt) bonds, "o-balogen effecf", and the application to catalytic reactions, and (5) photo- and -thiol driven trans insertion of phenylacetylene into H-Pt bonds.