Regio- and Enantioselective Functionalization of Gaseous Alkanes via Nickel-Catalyzed Alkene Dicarbofunctionalization

Abstract The regio- and enantioselective functionalization of gaseous alkanes remains an unsolved challenge in organic synthesis. Here, we report a general strategy for the asymmetric three-component dicarbofunctionalization of alkenes using readily available gaseous alkanes, including ethane, propane, and isobutane. This transformation, enabled by the merger of hydrogen atom transfer photocatalysis with a chiral nickel catalyst, efficiently delivers chiral α-aryl carbonyl compounds in good yield with excellent regio- and enantioselectivity (up to >20:1 rr and 99:1 er). Experimental and computational studies reveal insights into the mechanism controlling selectivity. Operating under exceptionally mild, energy-efficient conditions, the method unlocks a versatile platform for upgrading feedstock gaseous alkanes into sought-after chiral building blocks.