Synthesis of Fused [1,2,3]-Triazoloheteroarenes via Intramolecular Azo Annulation of N‑Tosylhydrazones Catalyzed by 1,8-Diaza-bicyclo[5.4.0]undec-7-ene

The structural diversity of triazoloheteroarenes render this moiety an attractive synthon for drug discovery, C–H functionalization, and complexant design for minor actinide separations. While contemporary work has demonstrated the capacity to leverage downstream functional group interconversion of the triazolopyridine, a broadly applicable method tolerant of diverse heteroaryl constructs and pendant functionality to obtain triazoloheteroarenes remains under reported. In this work, the serendipitous discovery of a metal, azide, and oxidant free transformation of various heteroaryl N-tosylhydrazones of carbaldehydes and ketones to the corresponding [1,2,3]-triazoloheteroarene via intramolecular azo annulation using a substoichiometric amount of 1,8-diaza-bicyclo[5.4.0]­undec-7-ene is described. These results substantively improve upon previous approaches offering efficient access to the described heterocycles. Discovery of reaction conditions, method optimization, complexant, pyridine, and heteroarene substrate scope, as well as relevant scale-up reactions are reported herein.