Controllable Regiodivergent Alkynylation of 1,3‐Bis(Boronic) Esters Activated by Distinct Organometallic Reagents

1,3‐Bis(boronic) esters can be readily synthesized from alkylBpin precursors. Selective transformations of these compounds hold the potential for late‐stage functionalization of the remaining C−B bond, leading to a diverse array of molecules. Currently, there are no strategies available to address the reactivity and, more importantly, the controllable regiodivergent functionalization of 1,3‐bis(boronic) esters. In this study, we have achieved controllable regiodivergent alkynylation of these molecules. The regioselectivity has been clarified based on the unique chelation patterns observed with different organometallic reagents. Remarkably, this methodology effectively addresses the low reactivity of 1,3‐bis(boronic) esters and bridges the gap in radical chemistry, which typically yields only the classical products formed via stable radical intermediates. Furthermore, the compounds synthesized through this approach serve as potent building blocks for creating molecular diversity. An efficient method for controllable regiodivergent alkynylation of 1,3‐bis(boronic) esters using distinct organometallic reagents has been developed. Mechanistic studies revealed that unique chelation patterns are essential in determining selectivity. This approach overcomes the drawbacks associated with coupling reactions through radical mechanisms, which commonly yield the classical products reacting through stable radical species.