Selective Coupling of 1,2‐Bis‐Boronic Esters at the more

1,2-Bis-boronic esters are useful synthetic intermediates particularly as the two boronic esters can be selectively functionalized. Usually, the less hindered primary boronic ester reacts, but herein, we report a coupling reaction that enables the reversal of this selectivity. This is achieved through the formation of a boronate complex with an electron-rich aryllithium which, in the presence of an electron-deficient aryl nitrile, leads to the formation of an electron donor-acceptor complex. Following visible-light photoinduced electron transfer, a primary radical is generated which isomerizes to the more stable secondary radical before radical-radical coupling with the arene radical-anion, giving β-aryl primary boronic ester products. The reactions proceed under catalyst-free conditions. This method also allows stereodivergent coupling of cyclic cis-1,2-bis-boronic esters to provide trans-substituted products, complementing the selectivity observed in the Suzuki-Miyaura reaction.