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3,3-Sigmatropic Shifts of Allyl Group Along Cyclopentadiene Ring Perimeter

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Abstract

Reversible non-degenerate 3,3-sigmatropic shifts of the allyl group along the perimeter of the five-membered ring occurring with energy barriers ΔG°≠ = 28.5–30.2 kcal/mol (o-dichlorobenzene-d4) have been detected in the allyl derivatives of 5-methyl-1,2,3,4-tetramethoxycarbonylcyclopentadiene by NMR method. Using DFT B3LYP/6-311++G(d,p) method, it has been shown that degenerate migrations of the allyl group in the related 5-allyl-1,2,3,4,5-pentamethoxycarbonylcyclopentadiene should occur via 3,3-sigmatropic shift through transition states with conformation of a six-membered ring (chair or boat, with close barriers ΔG°≠ = 27.4 or 27.7 kcal/mol, respectively). The simulated higher barrier of alternative 1,5-sigmatropic shifts of the allyl group (ΔG°≠ = 30.8 kcal/mol) indicates the energy preference of the migrations via 3,3-shifts.

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Funding

This study was performed in the scope of the project part of the State Task from the Ministry of Education and Science of Russia (project no. 4.844.2017/4.6) and the Program of Fundamental Studies of Presidium of Russian Academy of Sciences no. 14 (“Theoretical and experimental investigation of the chemical bond nature and the mechanism of important chemical reaction and processes, state registration no. АААА-А18-118011290115-6, I.E. Mikhailov).

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Authors and Affiliations

  1. Institute of Physical and Organic Chemistry, Southern Federal University, 344090, Rostov-on-Don, Russia

    G. A. Dushenko, I. E. Mikhailov, O. I. Mikhailova, R. M. Minyaev & V. I. Minkin

  2. Federal Research Center “Southern Scientific Center of the Russian Academy of Sciences”, 344006, Rostov-on-Don, Russia

    I. E. Mikhailov

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  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 G. A. Dushenko.

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Dushenko, G.A., Mikhailov, I.E., Mikhailova, O.I. et al. 3,3-Sigmatropic Shifts of Allyl Group Along Cyclopentadiene Ring Perimeter. Russ J Gen Chem 90, 161–165 (2020). https://doi.org/10.1134/S1070363220020012

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  • DOI: https://doi.org/10.1134/S1070363220020012

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