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Conformational effects on the electronic structure and chemical reactivity of lignin modelp-quinone methides and benzyl cations

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Abstract

The electronic structure and its dependence on the conformation in typical lignin model intermediates, β-arylethericp-quinone methide {2-methoxy-4-[2-(2-methoxyphenoxy)]propylidene-2,5-cyclohexadien-1-one} and related benzyl cation has been determined on the basis of semi-empirical quantum chemical calculations. Electrostatic but not frontier orbital characteristics of lignin intermediates were demonstrated to be dependent on the conformation. Conformationally induced electrostatic non-equivalence of two possible routes of nucleophile approach to the reaction center may be the main cause of stereoselectivity of the reactions of quinone methides (but not related cations) with nucleophiles. Quinone methides and related cations also differ in their intramolecular charge transfer properties.

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Authors and Affiliations

  1. Department of Organic Chemistry, The Academy of Forestry, 194018, St. Petersburg, Russia

    S. M. Shevchenko & M. Ya. Zarubin

  2. School of Forestry, Auburn University, 36849, Auburn, AL, U.S.A.

    T. J. Elder

  3. Department of Quantum Chemistry, The State University, St. Petersburg, 198904, Russia

    S. G. Semenov

Authors
  1. S. M. Shevchenko
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  2. T. J. Elder
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  3. S. G. Semenov
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  4. M. Ya. Zarubin
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Correspondence to S. M. Shevchenko.

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Shevchenko, S.M., Elder, T.J., Semenov, S.G. et al. Conformational effects on the electronic structure and chemical reactivity of lignin modelp-quinone methides and benzyl cations. Res. Chem. Intermed. 21, 413–423 (1995). https://doi.org/10.1007/BF03052267

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  • DOI: https://doi.org/10.1007/BF03052267

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