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Brønsted Acid Catalyzed Monoalkylation of Anilines with Trichloroacetimidates

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    Brønsted Acid Catalyzed Monoalkylation of Anilines with Trichloroacetimidates
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    Department of Chemistry, 1-014 Center for Science and Technology, Syracuse University, Syracuse, New York 13244, United States
    *E-mail: [email protected] (J.D.C.).
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    The Journal of Organic Chemistry

    Cite this: J. Org. Chem. 2015, 80, 3, 1993–2000
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    https://doi.org/10.1021/jo5027222
    Published January 8, 2015
    Copyright © 2015 American Chemical Society
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    Abstract

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    Trichloroacetimidates are useful alkylating agents for aromatic amines, requiring only a catalytic amount of a Brønsted acid to facilitate the reaction. Monoalkylation predominates under these conditions. Electron-poor anilines provide superior yields, with electron-rich anilines sometimes showing competitive Friedel–Crafts alkylation. A single flask protocol with formation of the imidate in situ is demonstrated, providing a convenient method for the direct substitution of alcohols with anilines. Reaction with a chiral imidate favors a mechanism that proceeds through a carbocation intermediate.

    Copyright © 2015 American Chemical Society

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    Supporting Information

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    Copies of 1H NMR and 13C NMR spectra of new compounds as well as chiral HPLC data for compounds 5 and 7c. This material is available free of charge via the Internet at http://pubs.acs.org.

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    The Journal of Organic Chemistry

    Cite this: J. Org. Chem. 2015, 80, 3, 1993–2000
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jo5027222
    Published January 8, 2015
    Copyright © 2015 American Chemical Society
    Request reuse permissions

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