This paper presents the results of our investigations on the arylation of thiophene using the transition‐metal‐free “aryne coupling” methodology. The reaction was studied by both experiment and computation (density functional theory) and comparison with phenyllithium was established. In parallel, the effects of the ligand and the salt on the coupling reaction were examined. The results underline the remarkable effect of such additives on the coupling reaction and the potency of the method to construct hetaryl–aryl backbones which open up promising access to a wide range of heterobiaryl structures using the novel “Het‐Aryne” route.

We disclose, for the first time, an efficient route for the construction of various heterobiaryl backbones in fair to excellent yields using the Aryne coupling methodology. This study outlined the remarkable effect of external chelating ligands and salt additives on the heterocyclic partner reactivity in the aryne coupling reaction.

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The synthesis of fused heterocycles containing several heteroatoms such as benzoxadiazepine and benzotriazocine scaffolds is considered as a complicated task due to their complex and polyunsaturated structures. In this review, we report the different methods and strategies that have been considered over the last decades for their synthesis.