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The Triple Role of Fluoride Ions in Palladium-Catalyzed Suzuki–Miyaura Reactions: Unprecedented Transmetalation from [ArPdFL2] Complexes

Authors

  • Dr. Christian Amatore,

    Corresponding author
    1. Département de Chimie, Ecole normale Supérieure, UMR CNRS-ENS-UPMC 8640, 24 Rue Lhomond, 75231 Paris Cedex 5 (France)
    • Département de Chimie, Ecole normale Supérieure, UMR CNRS-ENS-UPMC 8640, 24 Rue Lhomond, 75231 Paris Cedex 5 (France)
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  • Dr. Anny Jutand,

    Corresponding author
    1. Département de Chimie, Ecole normale Supérieure, UMR CNRS-ENS-UPMC 8640, 24 Rue Lhomond, 75231 Paris Cedex 5 (France)
    • Département de Chimie, Ecole normale Supérieure, UMR CNRS-ENS-UPMC 8640, 24 Rue Lhomond, 75231 Paris Cedex 5 (France)
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  • Gaëtan Le Duc

    1. Département de Chimie, Ecole normale Supérieure, UMR CNRS-ENS-UPMC 8640, 24 Rue Lhomond, 75231 Paris Cedex 5 (France)
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  • CNRS, ENS, and UPMC are thanked for financial support.

Abstract

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Fluoride ions play three roles in the Suzuki–Miyaura reaction. They favor the reaction by formation of trans-[ArPdF(PPh3)2], which reacts with Ar′B(OH)2 in an unprecedented rate-determining transmetalation, and by promoting the reductive elimination from the trans-[ArPdAr′(PPh3)2] intermediate. Conversely, F disfavors the reaction by formation of unreactive anionic Ar′B(OH)n−3Fn (n=1–3), leading to two antagonistic effects of F in the transmetalation.

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