Copper‐Catalyzed Dehydrogenative Amidation of Light Alkanes

The functionalization of C‐H bonds in light alkanes, particularly to form C‐N bonds, remains a challenge. We report the dehydrogenative coupling of amides with these C1‐C4 hydrocarbons to form the N ‐alkyl amide products with t BuOO t Bu as the oxidant, and a copper catalyst ligated by a phenanthroline‐type ligand. The reactions occurred in good yields in benzene or supercritical carbon dioxide as solvents. This strategy allowed for the determination of the relative reactivity of these alkane C‐H bonds toward this amination process and showed, in contrast to prior work with larger alkanes, that the reactivity correlated with bond dissociation energies.