Metal-Free Cascade Formation of Intermolecular C-N Bonds Accessing Substituted Isoindolinones under Cathodic Reduction.

An electrochemical protocol for the construction of substituted isoindolinones via reduction/amidation of 2-carboxybenzaldehydes and amines has been realized. Under metal-free and external-reductant-free electrolytic conditions, the reaction achieves the cascade formation of intermolecular C-N bonds and provides a series of isoindolinones in moderate to good yields. The deuterium-labeling experiment proves that the hydrogen in the methylene of the product is mainly provided by HO in the system.

Direct electrochemical reductive amination between aldehydes and amines with a H/D-donor solvent.

A novel electrochemical synthesis protocol has been achieved for reductive amination between aldehydes and amines in undivided cells at room temperature. Under metal-free and external-reductant-free electrolysis conditions, various important secondary amine products are obtained in moderate-to-high yields. Deuterium-labeling experiments have demonstrated that low-toxicity DMSO acts both as a solvent and a H-donor in the reaction.

Electrochemical vicinal aminotrifluoromethylation of alkenes: high regioselective acquisition of β-trifluoromethylamines.

A novel vicinal aminotrifluoromethylation of alkenes using CFSONa as a trifluoromethyl precursor and acetonitrile as an N-nucleophile has been achieved by an electrooxidative strategy. The present electrochemical protocol achieves efficient and highly regioselective difunctionalization of C[double bond, length as m-dash]C bonds under metal-free and external oxidant-free electrolysis conditions, leading to a series of β-trifluoromethylamine compounds with good to excellent yields. It is confirmed that the reaction involves free radical processes since CF radicals are trapped by scavengers and the β-trifluoromethylated radical is trapped by BHT, and the deuterium-labeling experiments prove that the oxygen in the product comes from water.