Reductant‐Free Cross‐Electrophile Synthesis of Di(hetero)arylmethanes by Palladium‐Catalyzed Desulfinative C−C Coupling

An efficient Pd‐catalyzed one‐pot desulfinative cross‐coupling to access medicinally relevant di(hetero)arylmethanes is reported. The method is reductant‐free, and involves a sulfinate transfer reagent and a Pd‐catalyst mediating the union of two electrophilic coupling partners; a (hetero)aryl halide and a benzyl halide. We establish for the first time that benzyl sulfinates, generated in situ, undergo efficient Pd‐catalyzed desulfinative cross‐coupling with (hetero)aryl halides to generate di(hetero)arylmethanes. The reaction can be extended to benzylic pseudohalides derived from benzyl alcohols. The reactions are straightforward to perform and scalable, and all reaction components are commercially available. Benzylic halides and heteroaryl halides are directly coupled using Pd‐catalysis and a simple sulfinate transfer reagent. The reactions proceed by formation of an intermediate benzylic sulfinate, formed in situ, and deliver di(hetero)arylmethane products. The reactions use only commercial components, and no stoichiometric metal reductant is needed.