• Open Access

Arylation with Unsymmetrical Diaryliodonium Salts: A Chemoselectivity Study

Authors

  • Joel Malmgren,

    1. Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, 106 91 Stockholm (Sweden), Fax: (+46) 8-154908
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  • Dr. Stefano Santoro,

    1. Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, 106 91 Stockholm (Sweden), Fax: (+46) 8-154908
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  • Dr. Nazli Jalalian,

    1. Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, 106 91 Stockholm (Sweden), Fax: (+46) 8-154908
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  • Prof. Fahmi Himo,

    Corresponding author
    1. Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, 106 91 Stockholm (Sweden), Fax: (+46) 8-154908
    • Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, 106 91 Stockholm (Sweden), Fax: (+46) 8-154908

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  • Prof. Berit Olofsson

    Corresponding author
    1. Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, 106 91 Stockholm (Sweden), Fax: (+46) 8-154908
    • Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, 106 91 Stockholm (Sweden), Fax: (+46) 8-154908

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Abstract

Phenols, anilines, and malonates have been arylated under metal-free conditions with twelve aryl(phenyl)iodonium salts in a systematic chemoselectivity study. A new “anti-ortho effect” has been identified in the arylation of malonates. Several “dummy groups” have been found that give complete chemoselectivity in the transfer of the phenyl moiety, irrespective of the nucleophile. An aryl exchange in the diaryliodonium salts has been observed under certain arylation conditions. DFT calculations have been performed to investigate the reaction mechanism and to elucidate the origins of the observed selectivities. These results are expected to facilitate the design of chiral diaryliodonium salts and the development of catalytic arylation reactions that are based on these sustainable and metal-free reagents.

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