Established herein is a radical-mediated C–H alkylation of enamides with cyclopropanols. An environmentally benign catalytic system with iron salt and air is used to permit the oxidative coupling process. The protocol demonstrates a broad substrate scope, allowing the stereoselective synthesis of alkylated enamides. The value of this strategy is further reflected by late-stage diversification of complex cyclopropanol-containing molecules and downstream transformations. Mechanistic studies reveal the dual role of iron salt in the reaction.

Ruthenium-catalyzed heteroannulation between enamides and isocyanates has been realized as a complementary approach to conventional strategies for the synthesis of pyrimidin-4-ones.

Described herein is a distinctive approach to branched 1,3-dienes through oxidative coupling of two nucleophilic substrates, β-allenyl silanes, and hydrocarbons appending latent functionality by copper catalysis. Notably, C(sp 3 )− H dienylation proceeded in a regiospecific manner, even in the presence of competitive C−H bonds that are capable of occurring hydrogen atom transfer process, such as those located at benzylic and other tertiary sites, or adjacent to an oxygen atom. Control experiments support the intermediacy of functionalized alkyl radicals.

1,2-Oxazetidines have been utilized as formaldimine precursors for the direct aminomethylation of enamides under a Ru(ii) species.