Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 143, Issue 33, Pages 13401-13407Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.1c06553
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Funding
- University of Geneva
- Swiss National Science Foundation [200021_159199]
- French Agence Nationale de la Recherche [ANR-19-CE09-0020]
- Chimie ParisTech
- Institut Universitaire de France
- Agence Nationale de la Recherche (ANR) [ANR-19-CE09-0020] Funding Source: Agence Nationale de la Recherche (ANR)
- Swiss National Science Foundation (SNF) [200021_159199] Funding Source: Swiss National Science Foundation (SNF)
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A [Ni/Mg]-catalyzed orthogonal tandem polymerization has been developed, starting from enol phosphates and leading to 1,4-cis-polydienes with selectivities up to 99%. By simple structural modifications of the monomeric unit, elastomeric or crystalline materials can be obtained. This tandem approach provides a straightforward and efficient way to enforce diversity and selectivity in diene polymerization while retaining a fair degree of control.
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.
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