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Synthesis of bicyclic N,N-enaminals by cyclization of alk-4-ynals with aliphatic diamines in DMSO upon treatment with KOH

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Abstract

A cyclization of alk-4-ynals with aliphatic diamines in DMSO upon treatment with KOH was found to lead to bicyclic N,N-enaminals. The studies of this reaction showed that 1,3-diaminopropane and N-methyl-1,3-diaminopropane gave (E)-6-(arylmethylidene)octahydropyrrolo[1,2-a]pyrimidines in 45—78% yields, whereas 1,2-diaminoethane gave 5-(arylmethylidene)hexahydropyrrolo[1,2-a]imidazoles as mixtures of E- and Z-isomers in up to 75% total yield. The mechanism of these new cascade cyclization reactions includes formation of the equilibrium mixtures of imines and cyclic aminals with subsequent intramolecular hydroamination of the triple bond having considerable ionic character.

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Authors and Affiliations

  1. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991, Moscow, Russian Federation

    V. D. Gvozdev, K. N. Shavrin & O. M. Nefedov

Authors
  1. V. D. Gvozdev
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  2. K. N. Shavrin
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  3. O. M. Nefedov
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Correspondence to V. D. Gvozdev.

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Dedicated to Academician of the Russian Academy of Sciences M. P. Egorov on the occasion of his 60th birthday.

For preliminary communication, see Ref. 1.

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2430–2437, Novemer, 2013.

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Gvozdev, V.D., Shavrin, K.N. & Nefedov, O.M. Synthesis of bicyclic N,N-enaminals by cyclization of alk-4-ynals with aliphatic diamines in DMSO upon treatment with KOH. Russ Chem Bull 62, 2430–2437 (2013). https://doi.org/10.1007/s11172-013-0351-3

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  • DOI: https://doi.org/10.1007/s11172-013-0351-3

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