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Degenerate rearrangement of 9-isopropenyl-9,10-dimethyl-phenanthren-9-yl and 9,10-dimethyl-9-(trans-1-methylprop-1-en-1-yl)phenanthren-9-yl cations

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Abstract

1H NMR study has shown that long-lived 9-R-9,10-dimethylphenanthren-9-yl cations (R = isopropenyl, trans-1-methylprop-1-en-1-yl) generated in the system HSO3F-SO2ClF-CD2Cl2 at −130°C undergo degenerate rearrangement via 1,2-vinyl shifts (ΔG’ = 37 and 39 kJ/mol, respectively, at −88°C). Analysis of the geometric parameters of the initial structures and transition states calculated by the DFT method indicates that unfavorable steric factors are responsible for the sharp deceleration of 1,2-shifts of the isopropenyl and trans-1-methylprop-1-en-1-yl groups as compared to vinyl and cis-1-methylprop-1-en-1-yl groups, respectively.

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Authors and Affiliations

  1. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences, pr. Akademika Lavrent’eva 9, Novosibirsk, 630090, Russia

    V. G. Artamoshkin, V. A. Bushmelev, A. M. Genaev & V. G. Shubin

  2. Novosibirsk State Pedagogical University, Novosibirsk, Russia

    V. G. Artamoshkin

Authors
  1. V. G. Artamoshkin
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  2. V. A. Bushmelev
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  3. A. M. Genaev
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  4. V. G. Shubin
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Original Russian Text © V. G. Artamoshkin, V. A. Bushmelev, A. M. Genaev, V. G. Shubin, 2006, published in Zhurnal Organicheskoi Khimii, 2006, Vol. 42, No. 9, pp. 1279–1285.

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Artamoshkin, V.G., Bushmelev, V.A., Genaev, A.M. et al. Degenerate rearrangement of 9-isopropenyl-9,10-dimethyl-phenanthren-9-yl and 9,10-dimethyl-9-(trans-1-methylprop-1-en-1-yl)phenanthren-9-yl cations. Russ J Org Chem 42, 1257–1263 (2006). https://doi.org/10.1134/S1070428006090016

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  • DOI: https://doi.org/10.1134/S1070428006090016

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