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Pericyclic and Heteroelectrocyclic Mechanisms for the Cyclization of 1,3,5-Hexatrien-1-one and Its 6-Aza Analog

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Abstract

The cyclization of 1,3,5-hexatrien-1-one, 1, and the Z- and E-isomers of 1-aza-1,3-butadienylketene 3 were studied using the semiempirical AM1 and PM3 methods. Cyclizations of compounds 1 and Z-3 are shown to occur via a mono-rotation mechanism with barriers of 15.49 and 32.85 kcal/mol respectively. The reactions proceed via non-planar transition states which result from rotation of the methylene group for compound 1 and the imino group for compound Z-3. Cyclization of E-3 proceeds via a non-rotatory mechanism through a planar transition state. The activation barrier is 4.83 kcal/mol (AM1). The electronic structures of the initial and final states, and of some intermediate structures, including the transition states for the cyclization of compounds 1 and 3, were analyzed by the natural orbital method using HF/6-31G*//AM1 calculations. Energetic, structural, and orbital criteria indicate the heteroelectric mechanism for the cyclization of compound E-3 and the pericyclic mechanism for the cyclization of compounds 1 and Z-3.

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Authors and Affiliations

  1. Ural State Technical University, Ekaterinburg, 620002, Russia

    V. A. Bakulev & Yu. O. Subbotina

  2. Institute of Chemistry, Karl-Franzens-University Graz, A-8010, Graz, Austria

    V. M. F. Fabian

Authors
  1. V. A. Bakulev
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  2. Yu. O. Subbotina
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  3. V. M. F. Fabian
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Bakulev, V.A., Subbotina, Y.O. & Fabian, V.M.F. Pericyclic and Heteroelectrocyclic Mechanisms for the Cyclization of 1,3,5-Hexatrien-1-one and Its 6-Aza Analog. Chemistry of Heterocyclic Compounds 39, 1504–1515 (2003). https://doi.org/10.1023/B:COHC.0000014416.75284.9d

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