Diacyl Peroxide-Enabled Palladium-Catalyzed Oxidative Borylation-Acyloxylation of Enallenes: Homogeneous and Recyclable Heterogeneous Platforms.

Diacyl peroxides serve as dual-function oxidants and acyloxy sources in a Pd-catalyzed oxidative borylation-acyloxylation of enallenes. Under mild conditions, this protocol delivers stereodefined vinylboronate esters with high chemo- and stereoselectivity across 80+ examples of enallenes and diacyl peroxides. The method avoids external metal or quinone oxidants and is applicable to gram-scale synthesis, product derivatization, and recyclable heterogeneous Pd catalysis. DFT calculations support accessible oxypalladation pathways that converge before C-B bond-forming reductive elimination.