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Comparing the Enantioselective Power of Steric and Electrostatic Effects in Transition-Metal-Catalyzed Asymmetric Synthesis

Authors

  • Dr. Albert Poater,

    1. Department of Chemistry, University of Salerno, Via Ponte don Melillo, 84084 Fisciano (Italy), Fax: (+39) 089-969603
    2. Catalan Institute for Water Research (ICRA), H2O Building, Scientific and Technological Park of the University of Girona, Emili Grahit 101, 17003 Girona (Spain)
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  • Dr. Francesco Ragone,

    1. Department of Chemistry, University of Salerno, Via Ponte don Melillo, 84084 Fisciano (Italy), Fax: (+39) 089-969603
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  • Dr. Ronaldo Mariz,

    1. Institute of Organic Chemistry, University of Zürich, Winterthurerstrasse 190, 8057 Zürich (Switzerland)
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  • Prof. Dr. Reto Dorta,

    Corresponding author
    1. Institute of Organic Chemistry, University of Zürich, Winterthurerstrasse 190, 8057 Zürich (Switzerland)
    • Institute of Organic Chemistry, University of Zürich, Winterthurerstrasse 190, 8057 Zürich (Switzerland)
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  • Prof. Dr. Luigi Cavallo

    Corresponding author
    1. Department of Chemistry, University of Salerno, Via Ponte don Melillo, 84084 Fisciano (Italy), Fax: (+39) 089-969603
    • Department of Chemistry, University of Salerno, Via Ponte don Melillo, 84084 Fisciano (Italy), Fax: (+39) 089-969603
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Abstract

The current approach to improve and tune the enantioselective performances of transition-metal catalysts for asymmetric synthesis is mostly focused to modifications of the steric properties of the ancillary ligands of the active metal. Nevertheless, it is also known that electrostatic effects can have a remarkable role to promote selectivity in asymmetric synthesis. Using the Rh-catalyzed asymmetric 1,4-addition of phenylboronic acid to 2-cyclohexenone leading to chiral 3-phenylcyclohexanone as an example, we could show that high enantioselectivity can be indeed achieved using catalysts essentially based either on steric or electrostatic effects as the main source of enantioselective induction. In this contribution we suggest that the analysis of the surface of interaction between the catalyst and the substrate could be a useful tool to quantify the power of steric and electrostatic effects of catalysts.

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