A metal‐free convergent paired electrolysis strategy to synthesize benzylic amines through direct arylation of tertiary amines and benzonitrile derivatives at room temperature has been developed. This TEMPO‐mediated electrocatalytic reaction makes full use of both anodic oxidation and cathodic reduction without metals or stoichiometric oxidants, thus showing great potential and advantages for practical synthesis. This convergent paired electrolysis method provides a straightforward and powerful means to activate C−H bonds and realize cross‐coupling with cathodically generated species.

Am etal-free convergent paired electrolysis strategy to synthesize benzylic amines through direct arylation of tertiary amines and benzonitrile derivatives at room temperature has been developed. This TEMPO-mediated electrocatalytic reaction makes full use of both anodic oxidation and cathodic reduction without metals or stoichiometric oxidants, thus showing great potential and advantages for practical synthesis.This convergent paired electrolysis method provides as traightforwarda nd powerful means to activate CÀHb onds and realizecross-coupling with cathodically generated species.Benzylic amines are ubiquitous structural motifs among natural products and medicinal agents. [1] An ideal method to construct the building blocks is the direct cross-coupling of aryl compounds and amines. [2][3][4] Among the existing methods, transition-metal catalysis or stoichiometric oxidants are utilized to active the inert a-amino sp 3 CÀHb onds.I n2 011, MacMillan and co-workers disclosed abreakthrough method involving photoredox-catalyzed a-amino C À Ha rylation for the construction of benzylic amines from readily available tertiary amines and cyanoaromatics. [2a] Inspired by this pioneering work, highly efficient photoredox catalysis methods were successively developed for diverse CÀHb ond arylation reactions. [2b-g] Different metal-catalysis strategies were successfully developed by the groups of Li, [3a] Sames, [3b] Chen, [3c] Maes, [3d] Yu, [3e,f] Glorius, [3g] and Gong, [3h] using oxidative cross-dehydrogenative coupling,d irected CÀHb ond activation, and deprotonation-transmetalation. Impressively,chiral benzylic amines have been constructed through asymmetric deprotonation, [3c] and chiral phosphorus ligands enabled enantioselective C À Hactivation by palladium [3f,h] or rhodium catalysis. [3g] Recently,S hirakawa et al. discovered that the metal-free arylation of alkylamines with aryl halides can be promoted by an equivalent tert-butoxy radical precursor at 60 or 120 8 8C. [4] Despite these important and elegant advances, the metal-and stoichiometric-oxidant-free methods for the Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

A general method for the synthesis of phenols from electron-deficient aryl ammonium salts or heteroaryl ammonium salts under mild conditions was developed. Benzaldehyde oxime, acetohydroxamic acid, and hydroxylamine hydrochloride were investigated as hydroxide surrogates respectively. With these hydroxide surrogates, a series of phenols were prepared in yields of 20–98%.

Direct para-selective C(sp2)–H alkylation of electron-deficient arenes based on the electroreduction-enabled radical addition of alkyl bromides has been developed under mild conditions. In the absence of any metals and redox agents, the simple electrolysis system tolerates a variety of primary, secondary, and tertiary alkyl bromides and behaves as an important complement to the directed alkylation of the C(sp2)–H bond and the classic Friedel-Crafts alkylation. This electroreduction process provides a more straightforward, environmentally benign, and effective alkylation method for electron-deficient arenes.