Continuous-flow electrosynthesis of urea and oxalic acid by CO_(2)-nitrate reduction and glycerol oxidation

Urea and oxalic acid are critical component in various chemical manufacturing industries.However,achieving simultaneous generation of urea and oxalic acid in a continuous-flow electrolyzer is a challenge.Herein,we report a continuous-flow electrolyzer equipped with 9-square centime-ter-effective area gas diffusion electrodes(GDE)which can simultaneously catalyze the glycerol oxidation reaction in the anode region and the reduction reaction of CO_(2) and nitrate in the cathode region,producing oxalic acid and urea at both the anode and cathode,respectively.The current density at low cell voltage(0.9 V)remained above 18.7 mA cm^(-2) for 10 consecutive electrolysis cycles(120 h in total),and the Faraday efficiency of oxalic acid(67.1%) and urea(70.9%)did not decay.Experimental and theoretical studies show that in terms of the formation of C-N bond at the cathode,Pd-sites can provide protons for the hydrogenation process of CO_(2) and NO_(3)^(-),Cu-sites can promote the generation of *COOH and Bi-sites can stabilize *COOH.In addition,in terms of glycerol oxidation,the introduction of Cu and Bi into Pd metallene promotes the oxidation of hydroxyl groups and the cleavage of C-C bond in glycerol molecules,respectively.

N-Radical enabled cyclization of 1,n-enynes

Compared to the widely used carbon-centered radicals,N-radicals have been relatively unexplored owing to the lack of practical and convenient production methods.Over the past few years,benefitting from the resurgence of reliable and controllable radical chemistry,N-radicals have been produced via thermal decomposition,oxidants,metal salts,or electrocatalysis.Therefore,numerous N-radical enabled cyclization of 1,n-enynes methods have been developed,providing a versatile and concise synthetic platform for the preparation of complex cyclic systems and natural products containing elaborate ring frameworks.In this review,we will summarize recent advances in the promising field of radical chemistry focusing on the production methods of N-radicals and their cyclization patterns,associated mechanisms,unmet challenges,and future opportunities.

Radical denitrogenative transformations of polynitrogen heterocycles:Building C–N bonds and beyond

Polynitrogen heterocycles are readily available and have recently arisen as versatile synthons for the formation of various C-C and C-X bonds,and medicinally active nitrogen-containing heterocycles.Several cascade reactions,including annulation,radical cascade,and borylation reactions,have been reported in which polynitrogen heterocycles are applied as arylation reagents.The success of these exceptional reactions illustrates the great synthetic potential of polynitrogen heterocycles,which provides a direct and useful approach to arylation reactions and the synthesis of nitrogen-containing heterocycles.The use of photocatalysts to effectively transfer energy from visible light to non-absorbing compounds has gained increasing attention as this method allows for the mild and efficient generation of radicals in a controlled manner.This approach has thus led to new methods that involve unique bond formation reactions.In addition,the use of free radical intermediates stabilized by transition metal catalysts is a powerful way to construct new chemical bonds.The aim of this review is to highlight the rapidly expanding area of radical-initiated denitrogenative cascade reactions of polynitrogen heterocycles and elaborate on their mechanisms from a new perspective by using photocatalysis and metal-based catalysis.

A facile access for the C–N bond formation by transition metal-free oxidative coupling of benzylic C–H bonds and amides

Using 2,3-dichloro-5,6-dicyano-p-benzoquinone(DDQ)as the oxidant,we communicate an efficient oxidative C–N coupling of benzylic C–H bonds with amides to afford a series of amination products in good yields.A wide range of functional groups as well as various sulfonamides and carboxamides are well tolerated.Moreover,this reaction involves both the challenging C–H functionalization and C–N bond formation.