Diaryl Sulfoxides from Aryl Benzyl Sulfoxides: A Single PalladiumCatalyzed Triple Relay Process

A novel approach to produce diaryl sulfoxides from aryl benzyl sulfoxides is reported. Optimization of the reaction conditions was performed using high-throughput experimentation techniques. The [Pd(dba)(2)]/NiXantPhos catalyst system successfully promotes a triple relay process involving sulfoxide -arylation, CS bond cleavage, and CS bond formation. The byproduct benzophenone is formed by an additional palladium-catalyzed process. It is noteworthy that palladium-catalyzed benzylative CS bond cleavage of sulfoxides is unprecedented. A wide range of aryl benzyl sulfoxides, as well as alkyl benzyl sulfoxides with various (hetero)aryl bromides were employed in the triple relay process in good to excellent yields (85-99%). Moreover, aryl methyl sulfoxides, dibenzyl sulfoxides, and dimethylsulfoxide could be utilized to generate diaryl sulfoxides involving multiple catalytic cycles by a single catalyst.