Copper-catalyzed photoinduced carbonylation of C1-C3 gaseous alkanes.

The catalytic conversion of carbon monoxide (CO) provides an enormous opportunity to construct carbonyl-containing molecules. Among them, the direct carbonylation of C-H bonds on gaseous hydrocarbon feedstocks provides a straightforward approach to access industrially important short-chain carboxylic acid derivatives. Here, we report a general and mild direct carbonylation of methane, ethane, and propane under blue LED irradiation at ambient temperature, enabling the direct formation of short-chain carboxylic acid derivatives. Notably, the direct carbonylation of ethane offers the potential for a more cost-efficient route to produce MMA. The combination of copper reduction and chlorine radical released via a ligand-to-metal charge transfer (LMCT) process facilitates the activation of gaseous hydrocarbon in a mild and atom-economical mode.