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.

By merging electricity with sulfate, the Ritter-type amination of C(sp3)-H bonds is developed in an undivided cell under room temperature. This method features broad substrate generality (71 examples, up to 93% yields), high functional-group compatibility, facile scalability, excellent site-selectivity and mild conditions. Common alkanes and electron-deficient alkylbenzenes are viable substrates. It also provides a straightforward protocol for incorporating C-deuterated acetylamino group into C(sp3)-H sites. Application in the synthesis or modification of pharmaceuticals or their derivatives and gram-scale synthesis demonstrate the practicability of this method. Mechanistic experiments show that sulfate radical anion, formed by electrolysis of sulfate, served as hydrogen atom transfer agent to provide alkyl radical intermediate. This method paves a convenient and flexible pathway for realizing various synthetically useful transformations of C(sp3)-H bonds mediated by sulfate radical anion generated via electrochemistry.

We develop an electrochemical nickel-catalyzed aminomethylation of aryl bromides under mild conditions. The convergent paired electrolysis makes full use of anode and cathode processes, free of a terminal oxidant, a sacrificial anode, a metal reductant, and a prefunctionalized radical precursor. In addition, this method exhibits wide functional group tolerance (63 examples), including some sensitive substituents and aromatic heterocycles. This redox neutral cross coupling provides a more environmentally friendly and synthetic practical protocol for forging C(sp 2 )−C(sp 3 ) bonds.

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.