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Difunctionalisation of Arenes and Heteroarenes by Directed Metallation and Sulfoxide–Magnesium Exchange

Authors

  • Dr. Laurin Melzig,

    1. Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstr 5-13, Haus F, 81377 München (Germany), Fax: (+49) 89-2180-77680
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  • Dr. Christian B. Rauhut,

    1. Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstr 5-13, Haus F, 81377 München (Germany), Fax: (+49) 89-2180-77680
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  • Dipl.-Chem. Nikolaus Naredi-Rainer,

    1. Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstr 5-13, Haus F, 81377 München (Germany), Fax: (+49) 89-2180-77680
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  • Prof. Dr. Paul Knochel

    Corresponding author
    1. Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstr 5-13, Haus F, 81377 München (Germany), Fax: (+49) 89-2180-77680
    • Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstr 5-13, Haus F, 81377 München (Germany), Fax: (+49) 89-2180-77680
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Abstract

The aryl sulfoxide moiety allows an expedient two-step difunctionalisation of readily available diaryl sulfoxides. Highly functionalised 1,2,4-trisubstituted arenes and difunctionalised heteroarenes (furans, thiophenes, benzofurans and pyridines) were prepared in a two-step sequence, triggered by an aryl sulfoxide group. In the first step, the sulfoxide moiety acts as a metallation-directing group, allowing smooth ortho-magnesiation with TMPMgClLiCl (TMP=tetramethylpiperidine). After a quenching reaction with an electrophile, the resulting sulfoxide is converted into a second magnesium reagent with iPrMgClLiCl (sulfoxide–magnesium exchange), which can be trapped with various electrophiles. Highly chemoselective TMPMgClLiCl and iPrMgClLiCl are compatible with a broad range of functional groups (e.g., F, Cl, CF3, CN, CO2tBu, alkynyl, ethers, thioethers). Large-scale reactions (25–40 mmol) and the preparation of fully functionalised furans and thiophenes are also reported.

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