Cooperative Effect of Two Metals: CoPd(OAc)4-Catalyzed CH Amination and Aziridination

The first Co/Pd‐cocatalyzed intramolecular CH amination and aziridination reactions were developed. Sulfamate esters were converted to oxathiazinanes by using CoPd(OAc)4 as catalyst and PhI(OAc)2 as oxidant. The mutual presence of both Co and Pd is crucial for the catalytic activity. This combination of two metals with simple acetate ligands provides an economical alternative to the Rh‐catalyzed insertion of nitrenoids into CH bonds. Two are better than one: The first Co/Pd‐cocatalyzed intramolecular CH amination and aziridination reactions were developed. Sulfamate esters were converted to oxathiazinanes by using CoPd(OAc)4 as catalyst and PhI(OAc)2 as oxidant (see scheme); neither metal alone can catalyze CH amination. This combination of two metals with simple acetate ligands provides an economical alternative to Rh‐catalyzed insertion of nitrenoids into CH bonds.