Cyclization and cycloisomerization of ortho-aryl(ethynyl)arenes provide an easy direct access to fused polycyclic aromatic carbo- and heterocycles. This methodology has demonstrated an impressive progress in the recent years. The goal of this review is to give a comprehensive outlook on the synthetic potential, scope, limitations, and mechanistic aspects of the cyclization reactions. The material is arranged according to the activation method that can be used to induce cyclization: pyrolysis, metal catalysis, electrophilic activation, radical induction, base catalysis. Particular attention is paid to the specificity of ortho-ethynylbiaryls with a heterocyclic central core.
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Previously unknown 1,1-dicyclopropylhydrazine was obtained in two steps starting from dicyclopropylamine. It serves as a convenient starting material to tri- and tetracyclopropylhydrazines, which have not been described in the literature either. Tricyclopropylhydrazine was prepared in an overall four-step sequence featuring the de Meijere-Chaplinski modification of the Kulinkovich reaction as a key step. Tetracyclopropylhydrazine was obtained by the reductive amination of the cyclopropanone ethyl trimethylsilyl acetal with 1,1-dicyclopropylhydrazine or with the parent hydrazine. Synthetic utility of these cyclopropylhydrazine building blocks is presented as well.
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