Skeletal Rearrangements Resulting from Reactions of 1,6:2,3- and 1,6:3,4-Dianhydro-beta-D-hexopyranoses with Diethylaminosulphur Trifluoride

0369111 - ÚCHP 2012 RIV GB eng J - Článek v odborném periodiku
Karban, Jindřich - Císařová, I. - Strašák, Tomáš - Červenková Šťastná, Lucie - Sýkora, Jan
Skeletal Rearrangements Resulting from Reactions of 1,6:2,3- and 1,6:3,4-Dianhydro-beta-D-hexopyranoses with Diethylaminosulphur Trifluoride.
Organic & Biomolecular Chemistry. Roč. 10, č. 2 (2012), s. 394-403. ISSN 1477-0520. E-ISSN 1477-0539
Grant CEP: GA AV ČR IAA400720706
Výzkumný záměr: CEZ:AV0Z40720504
Klíčová slova: carbohydrates * x-ray crystallography * benzyloxy group
Kód oboru RIV: CF - Fyzikální chemie a teoretická chemie
Impakt faktor: 3.568, rok: 2012

A complete series of eight 1,6:2,3- and 1,6:3,4-dianhydro-beta-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.
Trvalý link: http://hdl.handle.net/11104/0203256