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Telomerisation of 1,3-Butadiene with 1,4:3,6-Dianhydrohexitols: An Atom-Economic and Selective Synthesis of Amphiphilic Monoethers from Agro-Based Diols

Authors

  • Jonathan Lai,

    1. Unité de Catalyse et Chimie du Solide, UMR CNRS 8181, Université Lille Nord de France, ENSCL, BP 90108, 59652 Villeneuve d'Ascq (France), Fax: (+33) 3-20-33-63-01
    2. Chimie Moléculaire et Formulation, EA 4478, Université Lille Nord de France, ENSCL, BP 90108, 59652 Villeneuve d'Ascq (France)
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  • Sandra Bigot,

    1. Unité de Catalyse et Chimie du Solide, UMR CNRS 8181, Université Lille Nord de France, ENSCL, BP 90108, 59652 Villeneuve d'Ascq (France), Fax: (+33) 3-20-33-63-01
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  • Dr. Mathieu Sauthier,

    Corresponding author
    1. Unité de Catalyse et Chimie du Solide, UMR CNRS 8181, Université Lille Nord de France, ENSCL, BP 90108, 59652 Villeneuve d'Ascq (France), Fax: (+33) 3-20-33-63-01
    • Unité de Catalyse et Chimie du Solide, UMR CNRS 8181, Université Lille Nord de France, ENSCL, BP 90108, 59652 Villeneuve d'Ascq (France), Fax: (+33) 3-20-33-63-01
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  • Dr. Valérie Molinier,

    Corresponding author
    1. Chimie Moléculaire et Formulation, EA 4478, Université Lille Nord de France, ENSCL, BP 90108, 59652 Villeneuve d'Ascq (France)
    • Chimie Moléculaire et Formulation, EA 4478, Université Lille Nord de France, ENSCL, BP 90108, 59652 Villeneuve d'Ascq (France)
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  • Dr. Isabelle Suisse,

    1. Unité de Catalyse et Chimie du Solide, UMR CNRS 8181, Université Lille Nord de France, ENSCL, BP 90108, 59652 Villeneuve d'Ascq (France), Fax: (+33) 3-20-33-63-01
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  • Prof.  Yves Castanet,

    1. Unité de Catalyse et Chimie du Solide, UMR CNRS 8181, Université Lille Nord de France, ENSCL, BP 90108, 59652 Villeneuve d'Ascq (France), Fax: (+33) 3-20-33-63-01
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  • Prof.  Jean-Marie Aubry,

    1. Chimie Moléculaire et Formulation, EA 4478, Université Lille Nord de France, ENSCL, BP 90108, 59652 Villeneuve d'Ascq (France)
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  • Prof.  André Mortreux

    1. Unité de Catalyse et Chimie du Solide, UMR CNRS 8181, Université Lille Nord de France, ENSCL, BP 90108, 59652 Villeneuve d'Ascq (France), Fax: (+33) 3-20-33-63-01
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Abstract

The telomerisation of 1,3-butadiene with a Pd/TPPTS catalytic system in water or an organic solvent was used for the synthesis of C8 ethers from isosorbide, an agro-based diol. The use of water/oil biphasic reaction conditions allowed the selective synthesis of monoethers with improved rates upon using inorganic bases as promotors. As isosorbide is a non-symmetric diol, the two hydroxyl groups display different reactivities. 2-O-substituted-monoethers were preferentially obtained if water was used as the solvent, whereas in DMSO 5-O-substituted monoethers were the major products. Complete conversions of isosorbide with up to 94 % monoether selectivities were obtained. The optimized reaction conditions were successfully applied to isomannide and isoidide for the selective synthesis of the derived ethers. An improved reactivity of the endo-hydroxy groups of isosorbide and isomannide versus the exo-hydroxy groups of isosorbide and isoidide was observed if the reaction was performed in DMSO instead of water.

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