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A Bifunctional Copper Catalyst Enables Ester Reduction with H2: Expanding the Reactivity Space of Nucleophilic Copper Hydrides

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    A Bifunctional Copper Catalyst Enables Ester Reduction with H2: Expanding the Reactivity Space of Nucleophilic Copper Hydrides
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    • Birte M. Zimmermann
      Birte M. Zimmermann
      Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 115, 10623 Berlin, Germany
      More by Birte M. Zimmermann
    • Trung Tran Ngoc
      Trung Tran Ngoc
      Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 115, 10623 Berlin, Germany
      Institut für Chemie, Technische Universität Chemnitz, Straße der Nationen 62, 09111 Chemnitz, Germany
      More by Trung Tran Ngoc
    • Dimitrios-Ioannis Tzaras
      Dimitrios-Ioannis Tzaras
      Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 115, 10623 Berlin, Germany
      Institut für Chemie, Technische Universität Chemnitz, Straße der Nationen 62, 09111 Chemnitz, Germany
      More by Dimitrios-Ioannis Tzaras
    • Trinadh Kaicharla
      Trinadh Kaicharla
      Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 115, 10623 Berlin, Germany
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    • Johannes F. Teichert*
      Johannes F. Teichert
      Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 115, 10623 Berlin, Germany
      Institut für Chemie, Technische Universität Chemnitz, Straße der Nationen 62, 09111 Chemnitz, Germany
      *Email [email protected]
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      Orcidhttps://orcid.org/0000-0003-1043-8092
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2021, 143, 40, 16865–16873
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    https://doi.org/10.1021/jacs.1c09626
    Published October 4, 2021
    Copyright © 2021 The Authors. Published by American Chemical Society
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    Abstract

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    Employing a bifunctional catalyst based on a copper(I)/NHC complex and a guanidine organocatalyst, catalytic ester reductions to alcohols with H2 as terminal reducing agent are facilitated. The approach taken here enables the simultaneous activation of esters through hydrogen bonding and formation of nucleophilic copper(I) hydrides from H2, resulting in a catalytic hydride transfer to esters. The reduction step is further facilitated by a proton shuttle mediated by the guanidinium subunit. This bifunctional approach to ester reductions for the first time shifts the reactivity of generally considered “soft” copper(I) hydrides to previously unreactive “hard” ester electrophiles and paves the way for a replacement of stoichiometric reducing agents by a catalyst and H2.

    Copyright © 2021 The Authors. Published by American Chemical Society

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    This article is cited by 30 publications.

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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2021, 143, 40, 16865–16873
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.1c09626
    Published October 4, 2021
    Copyright © 2021 The Authors. Published by American Chemical Society
    Request reuse permissions

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