A selective metal–halogen exchange/electrophilic quench protocol on 4, 4′- dibromobiphenyl 4 that proceeds under non-cryogenic conditions is reported. This method provides an economic alternative to traditional transition-metal catalyzed cross-coupling chemistry to prepare various biaryls 7a–g. This novel route to functionalized biaryls was used as the basis for the kg-scale preparation of a biphenyl ketone 1, a key intermediate ...