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

Abstract

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.

Aryl carbonyls and carbinols as proelectrophiles for Friedel–Crafts benzylation and alkylation

“…A specialized variant, benzylation, is oen used for the production of 1,1-diarylalkanes 2 and 1,1,1-triarylalkanes 3 which play important roles in pharmaceuticals, 4 electroactive polymers, 5 and as dyes. 6 Other protocols frequently used to access these polyaryl alkane species typically call for transition metal-catalyzed [7][8][9][10][11][12][13][14][15] or base promoted 16 cross coupling between appropriate benzyl/aryl halides and benzyl/aryl nucleophiles.…”

Catalyst-free intramolecular radical cyclization cascades initiated by the direct homolysis of Csp3–Br under visible light

“…Considering that C sp 3 –C sp 3 bond formation is a part of almost all synthetic efforts, 10 a C sp 3 –Br bond is introduced as the first domino of the cyclization cascade (Scheme 1C). 11 However, direct alkylation involving alkyl bromide usually requires the catalysis of transition metals or photocatalysts (Ru, Ir, Acr + , etc .) to perform the electron transfer process.…”