Oxidative Cleavage and Ammoxidation of Unsaturated Hydrocarbons via Heterogeneous Auto-Tandem Catalysis

[Image: see text] The oxidative cleavage and functionalization of unsaturated C–C bonds are important processes for synthesis of carbonyl compounds from hydrocarbon feedstocks, yet there has been no report of direct amidation of unsaturated hydrocarbons via an oxidative cleavage of unsaturated C–C bonds with molecular oxygen as an environmentally benign oxidant. Herein, for the first time, we describe a manganese oxide-catalyzed auto-tandem catalysis strategy that enables direct synthesis of amides from unsaturated hydrocarbons by coupling oxidative cleavage with amidation. With oxygen as an oxidant and ammonia as a nitrogen source, a wide range of structurally diverse mono- and multisubstituted activated and unactivated alkenes or alkynes can smoothly undergo unsaturated C–C bond cleavage to deliver one- or multiple-carbon shorter amides. Moreover, a slight modification of the reaction conditions also allows for the direct synthesis of sterically hindered nitriles from alkenes or alkynes. This protocol features excellent functional group tolerance, a broad substrate scope, flexible late-stage functionalization, facile scalability, and a cost-effective and recyclable catalyst. Detailed characterizations reveal that the high activity and selectivity of the manganese oxides are attributed to the large specific surface area, abundant oxygen vacancies, better reducibility, and moderate acid sites. Mechanistic studies and density functional theory calculations indicate that the reaction proceeds through divergent pathways depending on the structure of substrates.