Rational synthesis of benzimidazole[3]arenes by CuII-catalyzed post-macrocyclization transformation
Shohei Tashiro1, Tsutomu Umeki1, Ryou Kubota1
1Department of Chemistry , Graduate School of Science , The University of Tokyo , 7-3-1 Hongo , Bunkyo-ku , Tokyo 113-0033 , Japan .
Abstract:
A new series of calix[n]arene analogues, benzimidazole[3]arenes, was rationally synthesized by CuII-catalyzed post-macrocyclization transformation of a tris(o-phenylenediamine) macrocycle, and fully characterized by NMR, MS, and single-crystal X-ray diffraction (XRD) analyses. The resulting syn- and anti-benzimidazole[3]arenes have a bowl-shaped and a warped structure, respectively, in their crystalline states, and both display a dynamic inversion behavior in solution. This modification resulted in strong fluorescence due to the generated benzimidazole moieties. The mechanistic study of the post-macrocyclization transformation demonstrated that the formation of both benzimidazole[3]arenes was catalyzed, via triimine intermediates, by CuII ions in air through oxidation and cyclization of the tris(o-phenylenediamine) macrocycle.
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