Abstract
A one-pot synthesis of arylmethylidene-substituted 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazoles based on the reaction of alk-4-ynals with 1,2-diaminobenzenes in DMSO at sequential catalysis with NH4Br and bases was suggested. The use in these processes of KOH as a base led to the selective formation of E-isomers of the final products in 48–66% yields, whereas less basic K2CO3 gave the corresponding Z-isomers in 32–82% yields. Similar cyclization reactions involving 2,3-diaminopyridine gave 7,8-dihydro-6H-pyrrolo[1’,2’:1,2]imidazo[4,5-b]pyridines in up to 56% yields. The distinguishing feature of the processes under study is proceeding of their key step that is intramolecular hydroamination of the triple bond, as a 5-exo-dig-cyclization. The necessity for the application of drastic conditions required for these processes is in agreement with the results of quantum chemical calculations of PES of their most probable rate-determining step, namely, the cyclization of the corresponding benzimidazolide anions to cyclic vinyl anions.
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For preliminary communication, see Ref. 1.
Based on the materials of the IV All-Russian Conference on Organic Chemistry and XVII Youth School-Conference on Organic Chemistry (November 22–27, 2015, Moscow, Russia).
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1829–1838, July, 2016.
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Gvozdev, V.D., Shavrin, K.N., Baskir, E.G. et al. Cyclization of alk-4-ynals with o-diaminoarenes as a selective one-pot synthesis of arylmethylidene-substituted 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazoles and 7,8-dihydro-6H-pyrrolo[1’,2’:1,2]imidazo[4,5-b]pyridines. Russ Chem Bull 65, 1829–1838 (2016). https://doi.org/10.1007/s11172-016-1517-6
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DOI: https://doi.org/10.1007/s11172-016-1517-6