Arylation, vinylation and alkylation of a wide range of NH/OH/SH substrates by oxidative cross-coupling with boronic acids in the presence of catalytic cupric acetate, weak base and in air (open-flask chemistry). The reaction works for amides, amines, amidines, anilines, azides, azoles, hydantoins, hydrazines, imides, imines, nitroso, pyrazinones, pyridines, purines, pyrimidines, sulfonamides, sulfinates, sulfoximines, ureas, alcohols, phenols, thiols, etc. The boronic acids can be replaced with siloxanes, stannanes or other organometalloids. The mild condition of this reaction is an advantage over Buchwald–Hartwig′s Pd-catalyzed cross-coupling using halides, though boronic acids are more expensive than halides. The Chan–Lam C–X bond cross-coupling reaction has emerged as a powerful and popular methodogy like Suzuki–Miyaura′s C–C bond cross-coupling reaction.