The synthesis of a broad variety of hetero- and carbocyclic scaffolds via a Pd-catalyzed domino Heck/SO2 insertion reaction is reported. This reaction utilizes DABSO, a safe and easy-to-handle alternative to SO2 gas. The reaction proceeds through a sulfinate intermediate, which can act as a lynchpin for the in situ generation of sulfones, sulfonamides, and sulfonyl fluorides. Good yields and scalability are demonstrated.

The first aminomethylation of oxabenzonorbornadienes using dual photoredox/nickel catalysis has been disclosed. This cascade reaction allowed the preparation of the cis-aminomethyl dihydronaphthalenols without any prefunctionalization or any use of nucleophilic organometallic species. The control of the regio-and stereoselectivity might be explained by a sequence involving insertion of nickel(0) into the C−O bond followed by the formation of a π-allyl intermediate.