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 C1–C4 hydrocarbons to form N‐alkyl amide products with tBuOOtBu as oxidant, and a copper complex of a phenanthroline‐type ligand as catalyst. 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. The dehydrogenative amidation of light alkanes C1–C4 has been accomplished using copper catalysis. This strategy has allowed establishing the relative reactivity of the C−H bonds of gaseous alkanes, which correlates with bond dissociation energy values.