Tuning Proton-Electron Synergy for Electrooxidative Alkyne Annulation: Mechanistic Insights and Synthetic Application

Abstract Electrooxidative catalysis surfaced as a resource-economic and increasingly viable platform toward sustainable organic synthesis. It challenges the paradigm of using stoichiometric chemical reagents with the aid of electricity to enable traceless electron and proton transfers. Thereby, molecular synthesis can be inherently connected to the hydrogen evolution reaction, while avoiding waste formation in the form of stoichiometric by-products. Alkynes represent a widely occurring structural motif of outstanding relevance in molecular synthesis. The direct exploitation of alkynes toward the activation of otherwise inert C─H bonds sets the stage for innovative dehydrogenative annulations, allowing for the rapid construction of structurally complex compounds. Specifically, the merger with earth-abundant metal catalysis constitutes a promising advancement in the light of green chemistry, bearing unique potential to redefine chemical processing.