Currently, the general synthesis of 5‐aryl‐phenanthridin‐6‐ones relies on the involvement of metal catalysis. Despite the urgent demand for green alternatives, avoiding synthetic routes that require transition metals for key roles is still challenging. Electrochemical efforts employing a constant potential protocol in divided cells revealed a possible alternative to the catalytic approach. A constant current protocol, undivided cells, and a remarkably low supporting electrolyte concentration enable a novel access to N‐aryl‐phenanthridin‐6‐ones by anodic N,C bond formation using directly generated amidyl radicals. Easy accessible starting materials, a broad scope of applicable functional groups, good yields, and a very simple set‐up are the benefits of this sustainable method.

A novel electrochemical access to N,N′-diarylhydrazines is developed using commercial anilines, a simple setup, and an ecologically efficient electrolyte system.

Ac onstant current protocol, employing undivided cells, ar emarkably low supporting electrolyte concentration,i nexpensive electrode materials, and as traightforward precursor synthesise nabling an ovel access to Nprotected carbazoles by anodic N,C bond formation using directlyg enerated amidyl radicals is reported. Scalability of the reaction is demonstrateda nd an easy deblocking of the benzoyl protecting group is presented. Carbazole was first isolated and characterizedb yG raebea nd Glaser,w hich employed ah igh-boiling coal tar distillate, in 1872. [1] In the same year,B raun and Greiffr eported as ynthesis using aniline as starting material and intense heatingi nt he course of ad istillation process, [2] which was confirmed by Graebea nd additionally refined employing diphenylamine as substrate in order to achieveh igher yields. [3] The relevance of this compound class can be perceived when its potentialu se in the pharmaceutical sector [4] due to their anti-Alzheimer, [5] antibacterial, [6] fungicidal, [7] antitubercular, [8] antitumor properties, [9] or in the technicala ssignment [10] is taken into account. Since the discoveryo fc arbazole, reams of methods tackling different moieties in order to build up this particular scaffold were reported. [11] Onec onvenient and straightforward access is by ac yclizationr eactionv ia aC ,N bond formation. Classical strategies utilizingt his approach are usually in demando f metal catalysis (Pd, [12] Cu, [13, 14] Ir, [15] Rh [16]), oxidizers, [13] pre-functionalization, [17] or strongly elevated temperatures [18] which result in several drawbacks. On the one hand, leastwise stoichiometric amountso fo xidizers,t oxic and partially expensive metal complexes, and essential leaving groups evoke reagent Scheme1.Conventional approaches and our electrochemical access to Nprotectedc arbazoles. TFA = trifluoroacetic acid;EDC = 1,2-dichloroethane; CPE = constant potential electrolysis;CCE = constant current electrolysis.

A synthetic approach to the cyclic disulfide moiety of 3,5-diimido-1,2-dithiolane derivatives starting with readily available precursors including the electrochemical coupling of dithioanilides is developed. The electrochemical key step provides sustainable synthetic access in high yields, using a very simple electrolysis setup.