Fig. Overview of radical difunctionalization of alkynes and our bifunctional reagents mediated strategy difunctionalization of alkynes (Fig. ). Inspired by the above-mentioned seminal works and our previous reports on the radical difunctionalizations , we conceived the idea that aryl rings anchored to acetates via SO2 could serve as a potential bifunctional reagent. Theoretically, a singleelectron oxidation of the sulfonyl acetate generates a highly electrophilic radical, which can then be incorporated into alkynes via radical addition. Next, the nascent vinyl radical triggers a sequential Smiles rearrangement to yield the final difunctionalized products (Fig. ). If successful, two valuable functional groups, alkyl carboxylate and aryl rings would be installed across an alkyne, ultimately resulting in the formation of synthetically useful all-carbon tetrasubstituted alkenes which are commonly found in natural products, pharmaceuticals and organic functional materials (Fig.