Electroorganic synthesis is a powerful sustainable tool for achieving greener and more efficient chemical processes across various industries. By adhering to the principles of green chemistry, atom economy, and resource efficiency, electroorganic synthesis can play a pivotal role in addressing environmental concerns and promoting a more sustainable future for chemical production. This review focuses on the latest advancements in the emerging application of electrochemistry in C-N bond formation through C-H/N-H cross-coupling. The first part of the review describes the electrochemical amination of arenes using metal catalysis (Cu, Co, Ni) with directing groups on the arene moiety. The next section addresses the same type of electrochemical C-N bond formation on arenes without directing groups, which represents a more general strategy enabling the synthesis of anilines and various heterocyclic-bound arenes in high yields. Further developments on benzylic systems are also discussed. This is followed by developments in the combination of photocatalysis and electrochemistry to activate C-H bonds in arenes, alkanes, and benzylic systems, including the use of flow reactor configurations for these reactions.

Unsymmetrical urea derivatives are essential structural motifs in a wide array of biologically significant compounds. Despite the well-established methods for synthesizing symmetrical ureas, efficient strategies for the synthesis of unsymmetrical urea derivatives remain limited. In this study, we present a novel approach for the synthesis of unsymmetrical urea derivatives through the coupling of amides and amines. Utilizing hypervalent iodine reagent PhI(OAc)2 as a coupling mediator, this method circumvents the need for metal catalysts, high temperatures, and inert atmosphere. The reaction proceeds under mild conditions and demonstrates broad substrate scope, including various primary and secondary amines and primary benzamides. This protocol not only offers a practical and versatile route for synthesizing unsymmetrical ureas but also shows significant potential for the late-stage functionalization of complex molecules in drug development.

The regiochemical outcome of a cobalt(ii) catalysed C-H activation reaction of aminoquinoline benzamides with unsymmetrical 1,3-diynes under relatively mild reaction conditions can be steered through the choice of diyne. The choice of diyne provides access to either 3- or 4-hydroxyalkyl isoquinolinones, paving the way for the synthesis of more highly elaborate isoquinolines.

Pyrazole and its derivatives are important azole heteroarenes prevalent in pharmaceutical compounds and have been used as ligands for protein binding, making them valuable targets for synthetic applications. Herein we disclose an electrochemical intermolecular C-H/N-H oxidative annulation of 2-phenylpyrazoles with alkynes using a rhodium(iii) redox regime without any external metal oxidants in a water compatible solvent system. Both symmetrical and unsymmetrical alkynes were shown to be compatible with the optimized conditions.

Here we present an iridium catalysed C2-selective methylation of indoles using methyltrifluoroborate as a source of methyl group. The iridium catalyst selectively discriminates the indole C2 and C4 C-H bonds by coordination with a pivaloyl directing group.

Described herein is a decarbonylative tandem C-H bis-arylsulfenylation of indole at the C2 and C4 C-H bonds through the use of pentamethylcyclopentadienyl iridium dichloride dimer ([Cp*IrCl2](2)) catalyst and disulfides. A new sacrificial electron-rich adamantoyl-directing group facilitates indole C-H bis-functionalization with a traceless in situ removal. Various differently substituted disulfides can be easily accommodated in this reaction by a coordination to Ir(III) through the formation of six- and five-membered iridacycles at the C2 and C4 positions, respectively. Mechanistic studies show that a C-H activation-induced C-C activation is involved in the catalytic cycle.

Cobalt catalysis has become a powerful strategy for the synthesis of biologically important heterocyclic targets. Due to its ready availability and low cost, the use of this transition metal for heterocycles synthesis has been of special interest as witnessed by its use in a growing number of elegant synthesis studies. Herein we summarize recent developments in the synthesis of heterocycles using cobalt oxidative catalysis.

The use of inexpensive base metal catalysis to perform C H activation is an active field of research in organic synthesis. Described herein is a sustainable cobaltcatalyzed diastereoselective oxidative annulation/double C H activation of benzothiophene-[b]-1,1-dioxide with aminoquinolinamides under mild reaction conditions for the synthesis of annulated benzothiophenes.

Metal-catalyzed cross-coupling reactions are among the most important transformations in organic synthesis. However, the use of C−H activation for sp2 C−N bond formation remains one of the major challenges in the field of crosscoupling chemistry. Described herein is the first example of the synergistic combination of copper catalysis and electrocatalysis for aryl C−H amination under mild reaction conditions in an atom-and step-economical manner with the liberation of H2 as the sole and benign byproduct.