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.

We report the first electrochemical strategy to synthesize functionalizedn aphthalene derivatives through [4+ +2] annulation-rearrangement-aromatization from styrenes under mild conditions.T he electrolysis does not require metals,o xidants and high valence substrates,i ndicating the atom and step-economy ideals.T he dehydrodimer produced through [4+ +2] cycloaddition of 4-methoxy a-methyl styrene is isolated and proved to be the key intermediate for the following oxydehydrogenation to form carbon cation, whichu ndergoes rearrangement-aromatization to affordthe final products.This reaction represents ap owerful access to construct multisubstituted naphthalene blocks in as ingle step.

Chiral γ-amino alcohols are the prevalent structural motifs and building blocks in pharmaceuticals and bioactive molecules. Enantioselective hydrogenation of β-amino ketones provides a straightforward and powerful tool for the synthesis of chiral γ-amino alcohols, but the asymmetric transformation is synthetically challenging. Here, a series of tridentate ferrocene-based phosphine ligands bearing modular and tunable unsymmetrical vicinal diamine scaffolds were designed, synthesized, and evaluated in the iridium-catalyzed asymmetric hydrogenation of β-amino ketones. The system was greatly effective to substrates with flexible structure and functionality, and diverse β-tertiary-amino ketones and β-secondary-amino ketones were hydrogenated smoothly. The excellent reactivities and enantioselectivities were achieved in the asymmetric delivery of various chiral γ-amino alcohols with up to 99% yields, >99% ee values, and turnover number (TON) of 48,500. The gram-scale reactions with low catalyst loading showed the potential application in industrial synthesis of chiral drugs, such as (S)-duloxetine, (R)-fluoxetine, and (R)-atomoxetine.

Novel and homogeneous zirconium phosphonate-supported Pd catalysts with modest BET surface areas (25.6 and 24.7 m 2 g À1 ), high pore volumes (0.39 and 0.73 cc g À1 ) and nano-sized pores (1-10 nm) were prepared by embedding Na 2 PdCl 4 particles in an organosoluble, porous and layered zirconium phosphonate with a filiform architecture structure for the first time. In the homogeneous palladium-catalyzed Suzuki coupling reaction at room temperature, various substituted benzene bromides with phenylboronic acids were smoothly converted into corresponding biphenyl compounds (82-97% yields), even in cases of electron-rich derivatives. These supported homogeneous Pd catalysts could be quantitatively recovered by using a solid/ liquid separation technique and be highly active without loss of catalytic activity in three consecutive runs.

A metal-free photoredox catalyzed decarboxylative radical coupling of free-carboxylic acids and glyoxylic oximes was developed to synthesize α,β-diamino acids.