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Access to Highly Stereodefined 1,4-cis-Polydienes by a [Ni/Mg] Orthogonal Tandem Catalytic Polymerization
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    Access to Highly Stereodefined 1,4-cis-Polydienes by a [Ni/Mg] Orthogonal Tandem Catalytic Polymerization
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    • Daniele Fiorito
      Daniele Fiorito
      Department of Organic Chemistry, University of Geneva, 30 quai Ernest Ansermet, 1211 Geneva, Switzerland
    • Malaury Simon
      Malaury Simon
      Chimie ParisTech, PSL University, CNRS, Institut de Recherche de Chimie Paris, 75005 Paris, France
    • Christophe M. Thomas*
      Christophe M. Thomas
      Chimie ParisTech, PSL University, CNRS, Institut de Recherche de Chimie Paris, 75005 Paris, France
      *Email [email protected]
    • Clément Mazet*
      Clément Mazet
      Department of Organic Chemistry, University of Geneva, 30 quai Ernest Ansermet, 1211 Geneva, Switzerland
      *Email [email protected]
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2021, 143, 33, 13401–13407
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    https://doi.org/10.1021/jacs.1c06553
    Published August 11, 2021
    Copyright © 2021 American Chemical Society

    Abstract

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    A [Ni/Mg]-catalyzed orthogonal tandem polymerization has been developed starting from enol phosphates. Initial investigations conducted on branched 1,3-dienes as monomers enabled identification of a Mg-initiated polymerization process leading to 1,4-cis-polydienes. When aryl enol phosphates are used as monomers, the [Ni/Mg]-catalyzed tandem polymerization affords 1,4-cis-polydienes with selectivities up to 99%. Elastomeric or crystalline materials were obtained by simple structural modifications of the monomeric unit. This tandem approach appears as a straightforward and efficient way to enforce diversity and selectivity in diene polymerization while retaining a fair degree of control, just as observed for stepwise systems that are accessible through established time- and manpower-consuming synthetic procedures.

    Copyright © 2021 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.1c06553.

    • Experimental procedures, characterization of all new compounds, spectroscopic, spectrometric and SEC, DSC, and TGA analyses (PDF)

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    Cited By

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    This article is cited by 3 publications.

    1. Kanokon Upitak, Christophe M. Thomas. One-Pot Catalysis: A Privileged Approach for Sustainable Polymers?. Accounts of Chemical Research 2022, 55 (16) , 2168-2179. https://doi.org/10.1021/acs.accounts.2c00192
    2. Kevin Basemann, Bradley M. Schmidt, Aaron D. Sadow. Substituent-Enhanced Intermolecular Catalytic Ene-yne Metathesis for Efficient 1,3-Diene Synthesis. ACS Catalysis 2022, 12 (1) , 226-234. https://doi.org/10.1021/acscatal.1c04074
    3. Philippe-Alexandre Poisson, Gaël Tran, Céline Besnard, Clément Mazet. Nickel-Catalyzed Kumada Vinylation of Enol Phosphates: A Comparative Mechanistic Study. ACS Catalysis 2021, 11 (24) , 15041-15050. https://doi.org/10.1021/acscatal.1c04800

    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2021, 143, 33, 13401–13407
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.1c06553
    Published August 11, 2021
    Copyright © 2021 American Chemical Society

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