Intramolecular Hydroalkoxylation of Non-Activated C[DOUBLE BOND]C Bonds Catalysed by Zeolites: An Experimental and Theoretical Study

Authors

  • Prof. Elena Pérez-Mayoral,

    1. J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic v.v.i., Dolejškova 3, 182 23 Prague 8 (Czech Republic)
    2. Departamento de Química Inorgánica y Química Técnica, Facultad de Ciencias, UNED, Paseo Senda del Rey 9, 28040 Madrid (Spain)
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  • Dr. Ines Matos,

    1. J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic v.v.i., Dolejškova 3, 182 23 Prague 8 (Czech Republic)
    2. REQUIMTE, FCT-UNL, Lisboa (Portugal)
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  • Prof. Petr Nachtigall,

    1. Faculty of Science, Charles University in Prague, Hlavova 8, 128 43 Prague 2 (Czech Republic)
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  • Miroslav Položij,

    1. Faculty of Science, Charles University in Prague, Hlavova 8, 128 43 Prague 2 (Czech Republic)
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  • Prof. Isabel Fonseca,

    1. REQUIMTE, FCT-UNL, Lisboa (Portugal)
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  • Dr. Dana Vitvarová-Procházková,

    1. J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic v.v.i., Dolejškova 3, 182 23 Prague 8 (Czech Republic)
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  • Prof. Jiří Čejka

    Corresponding author
    1. J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic v.v.i., Dolejškova 3, 182 23 Prague 8 (Czech Republic)
    • J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic v.v.i., Dolejškova 3, 182 23 Prague 8 (Czech Republic)
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Abstract

The high activity and selectivity of zeolites in the cyclisation of unsaturated alcohols is reported for the first time; the details of a reaction mechanism based on quantum chemical calculations are also provided. The high efficiency of zeolites MFI, BEA and FAU in the cyclisation of unsaturated alcohols (cis-decen-1-ol, 6-methylhept-5-en-2-ol and 2-allylphenol) to afford oxygen-containing heterocyclic rings is demonstrated. The best catalytic performance is found for zeolites with the optimum concentration of Brønsted acid sites (ca. 0.2 mmol g−1) and the minimum number of Lewis acid sites. It is proposed that the efficiency of the catalysts is reduced by the existence of the so-called dual site, at which a molecule of unsaturated alcohol can simultaneously interact with two acid sites (an OH group with one and the double bond with the other Brønsted site), which increases the interaction strength. The formation of such adsorption complexes leads to a decrease in the catalyst activity because of (i) an increase in the reaction barrier, (ii) an unfavourable conformation and (iii) diffusion limitations. A new procedure for the preparation of tetrahydrofurans and pyrans over zeolite catalysts provides important oxygen-containing heterocycles with numerous applications.

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