Oxidative carbene organocatalysis, inspired from Vitamin B1 catalyzed oxidative activation from pyruvate to acetyl coenzyme A, have been developed as a versatile synthetic method. To date, the α-, β-, γ-, δ- and carbonyl carbons of (unsaturated)aldehydes have been successfully activated via oxidative N-heterocyclic carbene (NHC) organocatalysis. In comparison with chemical redox or photoredox methods, electroredox methods, although widely used in mechanistic study, were much less developed in NHC catalyzed organic synthesis. Herein, an iodide promoted electroredox NHC organocatalysis system was developed. This system provided general solutions for electrochemical single-electron-transfer (SET) oxidation of Breslow intermediate towards versatile transformations. Radical clock experiment and cyclic voltammetry results suggested an anodic radical coupling pathway.

A metal-free and external-oxidant-free electrosynthesis of β-acyloxy-γ-selenyl amines was developed. The cascade reaction is triggered by anodic oxidative generation of electrophilic selenium cation, followed by electrophilic addition to the unactivated alkene, and successive water promoted intramolecular acyl migration. The reactions gave the products in up to 98% yield with controllable regio-and diastereoselectivities. Different chemoselectivity towards cyclization products was also viable with N-Boc and N-Cbz substrates. Both batch chemistry and flow chemistry were available for scale-up synthesis with up to 91% yield.

An electrochemical initiated heteroaryltrifluoromethylation of allylic amine was developed. The cascade reaction involved anodic oxidation of Langlois reagent (CF3SO2Na) to generated CF3 radical, radical addition to the unactivated alkene, Smiles-type...

Eco-friendly, green and diastereoselective synthesis of CF3-containing spirocyclic indolines were successfully developed. The cascade reaction contains anode oxidative generation of CF3 radical, addition to indoles, followed by the intramolecular spirocyclization....