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Deprotonative Metalation of Chloro- and Bromopyridines Using Amido-Based Bimetallic Species and Regioselectivity-Computed CH Acidity Relationships

Authors

  • Dr. Katia Snégaroff,

    1. Chimie et Photonique Moléculaires, UMR 6510 CNRS, Université de Rennes 1, Bâtiment 10A, Case 1003, Campus Scientifique de Beaulieu, 35042 Rennes Cedex (France), Fax: (+33) 2-2323-6955
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  • Tan Tai Nguyen,

    1. Chimie et Photonique Moléculaires, UMR 6510 CNRS, Université de Rennes 1, Bâtiment 10A, Case 1003, Campus Scientifique de Beaulieu, 35042 Rennes Cedex (France), Fax: (+33) 2-2323-6955
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  • Nada Marquise,

    1. Chimie et Photonique Moléculaires, UMR 6510 CNRS, Université de Rennes 1, Bâtiment 10A, Case 1003, Campus Scientifique de Beaulieu, 35042 Rennes Cedex (France), Fax: (+33) 2-2323-6955
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  • Dr. Yury S. Halauko,

    Corresponding author
    1. Department of Electrochemistry of the Belarusian State University, 14 Leningradskaya Str., Minsk, 220030 (Belarus), Fax: (+375) 17-2264696
    • Department of Electrochemistry of the Belarusian State University, 14 Leningradskaya Str., Minsk, 220030 (Belarus), Fax: (+375) 17-2264696
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  • Philip J. Harford,

    1. Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW (United Kingdom), Fax: (+44) 1223-336362
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  • Dr. Thierry Roisnel,

    1. Sciences Chimiques de Rennes, UMR 6226 CNRS, Université de Rennes 1, Bâtiment 10B, Campus Scientifique de Beaulieu, 35042 Rennes Cedex (France)
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  • Dr. Vadim E. Matulis,

    1. Research Institute for Physico-Chemical Problems of Belarusian State Univ., 14 Leningradskaya Str. Minsk, 220030 (Belarus)
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  • Prof. Oleg A. Ivashkevich,

    1. Research Institute for Physico-Chemical Problems of Belarusian State Univ., 14 Leningradskaya Str. Minsk, 220030 (Belarus)
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  • Dr. Floris Chevallier,

    1. Chimie et Photonique Moléculaires, UMR 6510 CNRS, Université de Rennes 1, Bâtiment 10A, Case 1003, Campus Scientifique de Beaulieu, 35042 Rennes Cedex (France), Fax: (+33) 2-2323-6955
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  • Dr. Andrew E. H. Wheatley,

    Corresponding author
    1. Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW (United Kingdom), Fax: (+44) 1223-336362
    • Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW (United Kingdom), Fax: (+44) 1223-336362
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  • Dr. Philippe C. Gros,

    1. SOR, SRSMC, Nancy Université, CNRS, Boulevard des Aiguillettes;, 54506 Vandoeuvre-Lès-Nancy (France)
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  • Prof. Florence Mongin

    Corresponding author
    1. Chimie et Photonique Moléculaires, UMR 6510 CNRS, Université de Rennes 1, Bâtiment 10A, Case 1003, Campus Scientifique de Beaulieu, 35042 Rennes Cedex (France), Fax: (+33) 2-2323-6955
    • Chimie et Photonique Moléculaires, UMR 6510 CNRS, Université de Rennes 1, Bâtiment 10A, Case 1003, Campus Scientifique de Beaulieu, 35042 Rennes Cedex (France), Fax: (+33) 2-2323-6955
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Abstract

A series of chloro- and bromopyridines have been deprotometalated by using a range of 2,2,6,6-tetramethylpiperidino-based mixed lithium–metal combinations. Whereas lithium–zinc and lithium–cadmium bases afforded different mono- and diiodides after subsequent interception with iodine, complete regioselectivities were observed with the corresponding lithium–copper combination, as demonstrated by subsequent trapping with benzoyl chlorides. The obtained selectivities have been discussed in light of the CH acidities of the substrates, determined both in the gas phase and as a solution in THF by using the DFT B3LYP method.

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