title: Efficient isomerization of methyl arabinofuranosides into corresponding arabinopyranosides in presence of pyridine.
abstract: Fisher glycosylation, the oldest but efficient reaction towards alkyl glycosides, suffers nonetheless from lack of selectivity, especially when dealing with pentoses. In this case, a mixture of the four isomers, namely the furanosides and the pyranosides, is formed. According to previous studies, the rate and selectivity of the reaction depend greatly on the reaction time and the temperature. In this report, another factor was evaluated, the introduction of a weak nucleophilic base. Interestingly, addition of pyridine few hours after the reaction has started allowed rapid isomerization of the methyl pentofuranosides into its pyranoside counterparts. The reaction proceeds with great diastereoselectivity using arabinose, ribose, xylose and lyxose as starting pentoses. Corresponding methyl pyranosides were obtained as the sole isomers with yields ranging from 65% to 75%.
authors.affiliation: Ecole Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226, 11 Allée de Beaulieu, CS 50837, 35708 Rennes Cedex 7, France.
authors.forename: Sunchu
authors.initials: S
authors.lastname: Prabhakar
authors.affiliation: Ecole Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226, 11 Allée de Beaulieu, CS 50837, 35708 Rennes Cedex 7, France.
authors.forename: Loïc
authors.initials: L
authors.lastname: Lemiègre
authors.affiliation: Ecole Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226, 11 Allée de Beaulieu, CS 50837, 35708 Rennes Cedex 7, France.
authors.forename: Thierry
authors.initials: T
authors.lastname: Benvegnu
authors.affiliation: Department of Chemistry, Indian Institute of Science Education and Research, Pune 411 008, India.
authors.forename: Srinivas
authors.initials: S
authors.lastname: Hotha
authors.affiliation: Ecole Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226, 11 Allée de Beaulieu, CS 50837, 35708 Rennes Cedex 7, France.
authors.forename: Vincent
authors.initials: V
authors.lastname: Ferrières
authors.affiliation: Ecole Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226, 11 Allée de Beaulieu, CS 50837, 35708 Rennes Cedex 7, France. Electronic address: laurent.legentil@ensc-rennes.fr.
authors.forename: Laurent
authors.initials: L
authors.lastname: Legentil
mesh_terms: D001089:Arabinose / Q000737:chemistry*; D006027:Glycosides / Q000138:chemical synthesis* / Q000737:chemistry; D006031:Glycosylation; D007536:Isomerism; D000432:Methanol / Q000737:chemistry*; D015394:Molecular Structure; D010429:Pentoses / Q000737:chemistry; D011725:Pyridines / Q000138:chemical synthesis / Q000737:chemistry*; D012266:Ribose / Q000737:chemistry; D014994:Xylose / Q000737:chemistry
chemical_list: D006027:Glycosides; D010429:Pentoses; D011725:Pyridines; C043333:lyxose; D012266:Ribose; D014994:Xylose; D001089:Arabinose; D000432:Methanol
keywords: Fisher glycosylation; Isomerization; Methyl pentosides