Abstract
The utility of reactions using unsymmetrically substituted aryne intermediates can be negatively impacted by issues with regioselectivity as these reactions are substrate controlled. This leaves no avenues for improving regioselectivity without altering the substrate which has led to numerous reports about how to enhance or reverse this regioselectivity in metal-free aryne reactions by changing the electronics. To the best of our knowledge, no such studies exist for systems with metal-bound aryne intermediates, which often suffer from worse regioselectivities. Herein we report a means of achieving regioselectivity in a metal-catalyzed aryne difunctionalization via catalyst control. Through the use of an unsymmetrical ligand environment, selectivity can be induced (up to 9:91 r.r.). These investigations demonstrate that catalyst design can influence selectivity in metal-catalyzed aryne reactions.