Dearomative bis-functionalization of quinoxalines and bis- N -arylation of (benz)imidazoles via Cu(II)-mediated addition of boronic acids.

A Cu(OTf) 2 -mediated regioselective dearomative aryl-hydroxylation across the C(sp 2 )N bond of 2-aryl quinoxalines and bis- N -arylation of (benz)imidazoles were developed using aryl boronic acids. For the dearomative aryl-hydroxylation, the C-center should be electrophilic ( ca. 0.08), the N-center nucleophilic ( ca. -0.50), and the C(sp 2 )N bond polarized (Δ e = 0.609).