title: Telomerisation of 1,3-butadiene with 1,4:3,6-dianhydrohexitols: an atom-economic and selective synthesis of amphiphilic monoethers from agro-based diols.
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.
authors.affiliation: Unité de Catalyse et Chimie du Solide, UMR CNRS 8181, Université Lille Nord de France, ENSCL, BP 90108, 59652 Villeneuve d'Ascq, France.
authors.forename: Jonathan
authors.initials: J
authors.lastname: Lai
authors.forename: Sandra
authors.initials: S
authors.lastname: Bigot
authors.forename: Mathieu
authors.initials: M
authors.lastname: Sauthier
authors.forename: Valérie
authors.initials: V
authors.lastname: Molinier
authors.forename: Isabelle
authors.initials: I
authors.lastname: Suisse
authors.forename: Yves
authors.initials: Y
authors.lastname: Castanet
authors.forename: Jean-Marie
authors.initials: JM
authors.lastname: Aubry
authors.forename: André
authors.initials: A
authors.lastname: Mortreux
mesh_terms: D002070:Butadienes / Q000737:chemistry*; D002384:Catalysis; D004987:Ethers / Q000138:chemical synthesis* / Q000737:chemistry; D007547:Isosorbide / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D010165:Palladium / Q000737:chemistry
chemical_list: D002070:Butadienes; D004987:Ethers; D010165:Palladium; C031763:1,3-butadiene; D007547:Isosorbide