Co-III-Catalyzed Isonitrile Insertion/Acyl Group Migration Between C-H and N-H bonds of Arylamides

A general efficient and site-selective cobalt-catalyzed insertion of isonitrile into C-H and N-H bonds of arylamides through C-H bond activation and alcohol assisted intramolecular trans-amidation is demonstrated. This straightforward approach overcomes the limitation by the presence of strongly chelating groups. Isolation of Co-III-isonitrile complex B has been achieved for the first time to understand the reaction mechanism.