Chemoselective Suzuki–Miyaura Cross‐Coupling via Kinetic Transmetallation

Chemoselective Suzuki–Miyaura cross‐coupling generally requires a designed deactivation of one nucleophile towards transmetallation. Here we show that boronic acids can be chemoselectively reacted in the presence of ostensibly equivalently reactive boronic acid pinacol (BPin) esters by kinetic discrimination during transmetallation. Simultaneous electrophile control allows sequential chemoselective cross‐couplings in a single operation in the absence of protecting groups. Set phases to stun: Chemoselective Suzuki–Miyaura cross‐coupling can be achieved by kinetic discrimination of boronic acids and BPin esters during transmetallation. Simultaneous electrophile control allows sequential chemoselective cross‐couplings in a single operation in the absence of protecting groups.