Boron-Catalyzed Hydroarylation of 1,3-Dienes with Arylamines

Catalytic hydroarylation reactions of conjugated dienes are achieved using tris(pentafluorophenyl)borane as a Lewis acid catalyst under mild reaction conditions. This new protocol shows a broad substrate scope for the highly regioselective functionalization of sterically hindered aniline derivatives. Experimental and extensive density functional theory mechanistic studies show that the complex of residual water and B(C6F5)(3) plays a crucial role in the aryl-assisted protonation of conjugated dienes, forming allyl cation intermediates that induce the facile electrophilic aromatic substitution of aniline substrates.

Automated summary

Catalytic hydroarylation reactions of conjugated dienes using tris(pentafluorophenyl)borane as a Lewis acid catalyst show a broad substrate scope for highly regioselective functionalization of sterically hindered aniline derivatives. Experimental and theoretical studies reveal the crucial role of residual water and B(C6F5)(3) complex in the reaction mechanism.