title: Skeletal rearrangements resulting from reactions of 1,6:2,3- and 1,6:3,4-dianhydro-β-D-hexopyranoses with diethylaminosulphur trifluoride.
abstract: A complete series of eight 1,6:2,3- and 1,6:3,4-dianhydro-β-D-hexopyranoses were subjected to fluorination with DAST. The 1,6:3,4-dianhydropyranoses yielded solely products of skeletal rearrangement resulting from migration of the tetrahydropyran oxygen (educts of D-altro and D-talo configuration) or of the 1,6-anhydro bridge oxygen (D-allo, D-galacto). The major products yielded by the 1,6:2,3-dianhydropyranoses were compounds arising from nucleophilic substitution, with configuration at C4 either retained (D-talo, D-gulo) or inverted (D-manno), or from C6 migration (D-allo). The minor products in the 1,6:2,3-series resulted from migration of the tetrahydropyran oxygen (D-gulo) or the oxirane oxygen (D-manno), or from nucleophilic substitution with retention of configuration (D-manno). The structure of most of the rearranged products was verified by X-ray crystallography.
authors.affiliation: Institute of the Chemical Process Fundamentals of the ASCR, v.v.i. Rozvojová 135, 165 02, Praha 6, Czech Republic. karban@icpf.cas.cz
authors.forename: Jindřich
authors.initials: J
authors.lastname: Karban
authors.forename: Ivana
authors.initials: I
authors.lastname: Císařová
authors.forename: Tomáš
authors.initials: T
authors.lastname: Strašák
authors.forename: Lucie Červenková
authors.initials: LČ
authors.lastname: Šťastná
authors.forename: Jan
authors.initials: J
authors.lastname: Sýkora
mesh_terms: D004048:Diethylamines / Q000737:chemistry*; D005461:Fluorine / Q000737:chemistry*; D005690:Galactose / Q000031:analogs & derivatives / Q000737:chemistry*; D008968:Molecular Conformation
chemical_list: D004048:Diethylamines; C458759:galactosan; D005461:Fluorine; C040394:diethylaminosulfur trifluoride; D005690:Galactose