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Evolution of a Multicomponent System: Computational and Mechanistic Studies on the Chemo- and Stereoselectivity of a Divergent Process

Authors

  • Salomé Llabrés,

    1. Department of Physical Chemistry and Institute of Biomedicine (IBUB), Faculty of Pharmacy, University of Barcelona, Avda Diagonal 643, 08028 Barcelona (Spain), Fax: (+34) 934035987
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  • Dr. Esther Vicente-García,

    1. Barcelona Science Park, Baldiri Reixac 10-12, 08028 Barcelona (Spain), Fax: (+34) 934037106
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  • Dr. Sara Preciado,

    1. Barcelona Science Park, Baldiri Reixac 10-12, 08028 Barcelona (Spain), Fax: (+34) 934037106
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  • Cristina Guiu,

    1. Barcelona Science Park, Baldiri Reixac 10-12, 08028 Barcelona (Spain), Fax: (+34) 934037106
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  • Prof. Ramon Pouplana,

    1. Department of Physical Chemistry and Institute of Biomedicine (IBUB), Faculty of Pharmacy, University of Barcelona, Avda Diagonal 643, 08028 Barcelona (Spain), Fax: (+34) 934035987
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  • Prof. Rodolfo Lavilla,

    Corresponding author
    1. Barcelona Science Park, Baldiri Reixac 10-12, 08028 Barcelona (Spain), Fax: (+34) 934037106
    2. Laboratory of Organic Chemistry, Faculty of Pharmacy, University of Barcelona, Avda Joan XXIII s/n, 08028 Barcelona (Spain)
    • Rodolfo Lavilla, Barcelona Science Park, Baldiri Reixac 10-12, 08028 Barcelona (Spain), Fax: (+34) 934037106

      F. Javier Luque, Department of Physical Chemistry and Institute of Biomedicine (IBUB), Faculty of Pharmacy, University of Barcelona, Avda Diagonal 643, 08028 Barcelona (Spain), Fax: (+34) 934035987

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  • Prof. F. Javier Luque

    Corresponding author
    1. Department of Physical Chemistry and Institute of Biomedicine (IBUB), Faculty of Pharmacy, University of Barcelona, Avda Diagonal 643, 08028 Barcelona (Spain), Fax: (+34) 934035987
    • Rodolfo Lavilla, Barcelona Science Park, Baldiri Reixac 10-12, 08028 Barcelona (Spain), Fax: (+34) 934037106

      F. Javier Luque, Department of Physical Chemistry and Institute of Biomedicine (IBUB), Faculty of Pharmacy, University of Barcelona, Avda Diagonal 643, 08028 Barcelona (Spain), Fax: (+34) 934035987

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Abstract

The evolution of a ternary molecular system (imine, diene and nitrile) is analyzed to disclose the pathways leading to a divergent synthetic outcome. The Lewis acid catalyzed reaction between cyclohexadiene, 2-phenyl-indol-3-one and acetonitrile yields the imino-Diels–Alder adduct as the major product together with minor amounts of the Mannich–Ritter-amidine product. The experimental and computational data show that the relative orientation of the initial reactants dictates the synthetic outcome. The exo approach between imine and diene leads to the Diels–Alder adduct in a concerted process, whereas the endo mode leads to a polarized intermediate, which is trapped by acetonitrile to yield the multicomponent adduct.

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