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Circumambulatory Rearrangements of 5-Halo-1,2,3,4,5-pentaphenylcyclopentadienes

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Abstract

DFT quantum chemical calculations at the CAM-B3LYP/Def2TZVP level of theory showed that intramolecular migrations of halogens in 5-halo-1,2,3,4,5-pentaphenylcyclopentadienes (C5Ph5Hlg, Hlg = F, Cl, Br, I) involve chiral conformation of their molecules with a propeller arrangement of phenyl groups via 1,5-sigmatropic shifts around the five-membered ring through asymmetric transition states with energy barriers ΔE≠ZPE of 42.5 (F), 26.2 (Cl), 20.2 (Br), and 15.2 kcal/mol (I). The results were consistent with the data of dynamic NMR spectroscopy. The P and M enantiomers are readily interconvertible (ΔE≠ZPE = 1.7–3.7 kcal/mol) by way of synchronous flips of the phenyl groups. The calculated barriers to alternative 1,3-halogen shifts in C5Ph5Hlg are considerably higher than those for 1,5-shifts: ΔE≠ZPE = 60.7 (F), 38.6 (Cl), 32.0 (Br), and 27.9 kcal/mol (I).

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Funding

This study was financially supported by the Southern Federal University, 2020 (Ministry of Science and Education of the Russian Federation).

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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 & V. I. Minkin

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  1. G. A. Dushenko
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  2. I. E. Mikhailov
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  3. V. I. Minkin
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Correspondence to G. A. Dushenko.

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Dushenko, G.A., Mikhailov, I.E. & Minkin, V.I. Circumambulatory Rearrangements of 5-Halo-1,2,3,4,5-pentaphenylcyclopentadienes. Russ J Org Chem 56, 1744–1752 (2020). https://doi.org/10.1134/S1070428020100127

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