The robustness of iron catalysis enabling the oxidative coupling reactions of enamides with formamides is described. Routing from readily accessible feedstocks, the efficient approach is implemented to furnish a broad array of value-added N-acyl enamine amide derivatives, which serve as versatile precursors of biologically relevant N-heterocycles including pyrimidin-4-ones and 4-hydroxypyridin-2-ones. Preliminary mechanistic studies supported the notion that this direct carbamoylation reaction proceeded through an aminoacyl radical species.

Direct oxidative C(sp)−H/C(sp3)−H cross‐coupling offers an ideal and environmentally benign protocol for C(sp)−C(sp3) bond formations. As such, reactivity and site‐selectivity with respect to C(sp3)−H bond cleavage have remained a persistent challenge. Herein is reported a simple method for iron‐catalyzed/silver‐mediated tertiary alkylation of terminal alkynes with readily available and versatile 1,3‐dicarbonyl compounds. The reaction is suitable for an array of substrates and proceeds in a highly selective manner even employing alkanes containing other tertiary, benzylic, and C(sp3)−H bonds alpha to heteroatoms. Elaboration of the products enables the synthesis of a series of versatile building blocks. Control experiments implicate the in situ generation of a tertiary carbon‐centered radical species.

We have presented a unique example of dehydrogenative acylation of enamides with aldehydes enabled by an earth-abundant iron catalyst. The protocol provides the straightforward access to valuable β-ketoenamides with ample substrate scope and excellent functional group tolerance. Notably, distinct C–H acylation of enamide rather than at N–H moiety site occurs with absolute Z-selectivity was observed. Late-stage modifications of complex molecules and versatile synthetic utility of β-ketoenamides further highlight the practicability of this transformation.

Direct oxidative C(sp)−H/C(sp3)−H cross‐coupling offers an ideal and environmentally benign protocol for C(sp)−C(sp3) bond formations. As such, reactivity and site‐selectivity with respect to C(sp3)−H bond cleavage have remained a persistent challenge. Herein is reported a simple method for iron‐catalyzed/silver‐mediated tertiary alkylation of terminal alkynes with readily available and versatile 1,3‐dicarbonyl compounds. The reaction is suitable for an array of substrates and proceeds in a highly selective manner even employing alkanes containing other tertiary, benzylic, and C(sp3)−H bonds alpha to heteroatoms. Elaboration of the products enables the synthesis of a series of versatile building blocks. Control experiments implicate the in situ generation of a tertiary carbon‐centered radical species.