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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
Author(s) -
Lai Jonathan,
Bigot Sandra,
Sauthier Mathieu,
Molinier Valérie,
Suisse Isabelle,
Castanet Yves,
Aubry JeanMarie,
Mortreux André
Publication year - 2011
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.201100135
Subject(s) - isosorbide , chemistry , reactivity (psychology) , diol , solvent , catalysis , organic chemistry , amphiphile , medicinal chemistry , medicine , alternative medicine , pathology , copolymer , polymer
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.