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Mechanisms of circumambulatory rearrangements of 5-halogeno-1,2,3,4,5-pentamethoxycarbonylcyclopentadienes

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Abstract

Possible paths of halogen atom migration in 5-halogeno-1,2,3,4,5-pentamethoxycarbonylcyclopentadienes were studied using the density functional theory. The calculations revealed preferential 1,5(in comparison with 1,3-) sigmatropic shifts of halogen atoms along the perimeter of the five-membered ring with the energy barriers ΔE ZPE ≠ = 42.9, 26.9, 19.8, and 15.4 kcal mol–1 for the fluoro-, chloro-, bromo-, and iodosubstituted derivatives, respectively. The calculated charges of halogen atoms in the structures of transition states for 1,5-shifts change from negative for the fluorine atom to positive for the iodine atom (–0.356 (F), 0.019 (Cl), 0.052 (Br), 0.184 e (I)). The migration capacity increases in the order F < Cl < Br < I with an increase in the atomic radius of halogen.

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Authors and Affiliations

  1. aSouthern Scientific Center of the Russian Academy of Sciences, 41 ul. Chekhova, 344006, Rostov-on-Don, Russian Federation

    G. A. Dushenko, I. E. Mikhailov & O. I. Mikhailova

  2. Southern Federal University, 105/42 ul. Bol’shaya Sadovaya, 344006, Rostov-on-Don, Russian Federation

    I. E. Mikhailov & V. I. Minkin

  3. Research Institute of Physical and Organic Chemistry, Southern Federal University, 194/2 prosp.Stachki, 344090, Rostov-on-Don, Russian Federation

    R. M. Minyaev & V. I. Minkin

Authors
  1. G. A. Dushenko
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  2. I. E. Mikhailov
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  3. O. I. Mikhailova
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  4. R. M. Minyaev
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  5. V. I. Minkin
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Correspondence to I. E. Mikhailov.

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Dedicated to Academician of the Russian Academy of Sciences N. S. Zefirov on the occasion of his 80th birthday.

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2043—2049, September, 2015.

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Dushenko, G.A., Mikhailov, I.E., Mikhailova, O.I. et al. Mechanisms of circumambulatory rearrangements of 5-halogeno-1,2,3,4,5-pentamethoxycarbonylcyclopentadienes. Russ Chem Bull 64, 2043–2049 (2015). https://doi.org/10.1007/s11172-015-1115-z

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  • DOI: https://doi.org/10.1007/s11172-015-1115-z

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