Hydrogen-Bond-Assisted Activation of Allylic Alcohols for Palladium-Catalyzed Coupling Reactions

Authors

  • Yasemin Gumrukcu,

    1. Van't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH, Amsterdam (The Netherlands), Fax: (+31) 20-525-5604
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  • Prof. Dr. Bas de Bruin,

    1. Van't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH, Amsterdam (The Netherlands), Fax: (+31) 20-525-5604
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  • Prof. Dr. Joost N. H. Reek

    Corresponding author
    1. Van't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH, Amsterdam (The Netherlands), Fax: (+31) 20-525-5604
    • Van't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH, Amsterdam (The Netherlands), Fax: (+31) 20-525-5604

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Abstract

We report direct activation of allylic alcohols using a hydrogen-bond-assisted palladium catalyst and use this for alkylation and amination reactions. The novel catalyst comprises a palladium complex based on a functionalized monodentate phosphoramidite ligand in combination with urea additives and affords linear alkylated and aminated allylic products selectively. Detailed kinetic analysis show that oxidative addition of the allyl alcohol is the rate-determining step, which is facilitated by hydrogen bonds between the alcohol, the ligand functional group, and the additional urea additive.

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