The current report represents a transition‐metal‐free synthesis of oxazoline and isoxazoline derivatives by a tandem electro‐oxidative chalcogenation‐cyclization process. Both C−Se and C−S bond‐forming protocols were developed without using any external oxidant and the reaction was performed at room temperature, open to the air. Using this methodology, 29 substituted oxazoline and 16 substituted isoxazoline derivatives were synthesized with up to 91% isolated yield.

An electrochemical method for the synthesis of unsymmetrically substituted NH-pyrroles is described. The synthetic strategy comprises ac hallenging heterocoupling between two structurally diverse enamines via sequential chemoselective oxidation, addition, and cyclization processes. As eries of aryl-and alkyl-substituted enamines were effectively cross-coupled from an equimolar mixture to synthesize various unsymmetrical pyrrole derivatives up to 84 %y ield. The desired cross-coupling was achieved by tuning the oxidation potential of the enamines by utilizing a" magic effect" of the additive trifluoroethanol (TFE). Additionally, extensive computational studies reveal the unique role of TFE in promoting the heterocoupling process by regulating the activation energies of the reaction steps through H-bonding and CÀH•••p interactions.I mportantly,t he developed electrochemical protocol was found to be equally efficient for the homocoupling of enamines to form symmetric pyrroles up to 92 %y ield.

An efficient synthetic route for the construction of N 2 -aryl 1,2,3-triazoles is reported via sequential C−N bond formation and electro-oxidative N−N coupling under metal-free conditions. Readily accessible 2-aminoacrylates and aryldiazonium salts were used as starting materials, and the developed protocol displays excellent functional group tolerance, allowing an extensive range of substrate scope up to 91% isolated yield. Various mechanistic studies, along with the isolation of an intermediate adduct, refer to successive ionic and radical reaction sequences.N itrogen-containing heterocyclic compounds are among the most used structural motifs in biological and material sciences due to their diverse properties. 1 Specifically, N-aryl 1,2,3-triazoles are important molecular scaffolds present in various drugs and biologically active compounds like xanthine oxidase inhibitors, numerous antibacterial and anti-influenza agents, etc. (Figure 1). 2

Intramolecular electro-oxidative addition of enamines or amides to nonactivated alkynes was attained to access carbonyl-pyrroles or -oxazoles from N-propargyl derivatives. Organoselenium was employed as the electrocatalyst, which played a crucial role as a π-Lewis acid and selectively activated the alkyne for the successful nucleophilic addition. The synthetic strategy permits a wide range of substrate scope up to 93% yield. Several mechanistic experiments, including the isolation of a seleniumincorporated intermediate adduct, enlighten the electrocatalytic pathway.

An electrochemical method for the synthesis of unsymmetrically substituted NH-pyrroles is described. The synthetic strategy comprises ac hallenging heterocoupling between two structurally diverse enamines via sequential chemoselective oxidation, addition, and cyclization processes. As eries of aryl-and alkyl-substituted enamines were effectively cross-coupled from an equimolar mixture to synthesize various unsymmetrical pyrrole derivatives up to 84 %y ield. The desired cross-coupling was achieved by tuning the oxidation potential of the enamines by utilizing a" magic effect" of the additive trifluoroethanol (TFE). Additionally, extensive computational studies reveal the unique role of TFE in promoting the heterocoupling process by regulating the activation energies of the reaction steps through H-bonding and CÀH•••p interactions.I mportantly,t he developed electrochemical protocol was found to be equally efficient for the homocoupling of enamines to form symmetric pyrroles up to 92 %y ield.