Harnessing Bromo/Acyloxy Transposition (BrAcT) and Excited-State Copper Catalysis for Styrene Difunctionalization.

1,2-Difunctionalization of styrenes, adding two distinct functional groups across the C═C double bond, has emerged as a powerful tool for enhancing molecular complexity. Herein, we report the development of a regioconvergent β-acyloxylation-α-ketonylation of styrenes through bromo/acyloxy transposition (BrAcT) and excited-state copper catalysis. This approach is amenable to gram-scale synthesis and tolerates a wide range of functional groups and complex molecular frameworks, including derivatives of natural products and marketed drugs. Our experimental and computational studies suggest a unique mechanism featuring a dynamic, ionic BrAcT process and excited-state copper-catalyzed redox reactions. We anticipate that this BrAcT process could serve as a broadly applicable and versatile strategy for β-acyloxylation-α-functionalization of styrenes, creating valuable intermediates for preparing new pharmaceuticals, agrochemicals, and functional materials.