Abstract
<jats:p>Ozonolysis and Baeyer-Villiger (BV) rearrangement are amongst the earliest transformations, where cyclic/acyclic-peroxo intermediates, often known as Criegee intermediate has been detected. Herein, we are disclosing the merger of Criegee intermediate with C(sp3)-C(sp3) cross coupling via a rare anti-Giese addition for a new genre of C−C cross coupling to access complex chemical libraries. Detailed mechanistic investigation reveals the generation of cyclic tetrahedral peroxo intermediate (CI) and gas-phase analysis establishes the formation of 16O=C=O18 under 18O2 condition, straightforwardly supports the formation of peroxylactones via Criegee intermediate under our standard conditions. The method proceeds via cyclic ether/acetal activation, aerial oxidation at benzylic position and decarboxylation in a cascade manner to yield cyclic ether/acetal-functionalized ketones in moderate to excellent yields. Importantly, many pharmaceutically active drug-like molecules have been screened thoroughly, which establish excellent tolerance and high regio-selectivity for present methodology.</jats:p>