Palladium-Catalyzed Domino Heck/Sulfination: Synthesis of Sulfonylated Hetero- and Carbocyclic Scaffolds Using DABCO-Bis(sulfur dioxide).

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.

Aminomethylation of Oxabenzonorbornadienes via the Merger of Photoredox and Nickel Catalysis.

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.