title: An improved synthesis of 3,6-anhydro-D-glucal and a study of its unusual chemical reactivity.
abstract: 6-O-Tosyl-d-glucal 1 upon treatment with excess LiAlH4 unexpectedly gave 3,6-anhydro-d-glucal 2 as a major product in good yield. A crystal structure was obtained. Reaction of the anhydride 2 with N-iodosuccinimide (NIS) in excess methanol resulted in the formation of diastereomeric 2-deoxy-2-iodoglycosides. Addition of ceric (IV) ammonium nitrate and thiophenol to a solution of 2 in acetonitrile gave a mixture of 2-deoxy and 2,3-unsaturated thioglycosides. Reaction of 1,2:3,4-di-O-isopropylidine-α-d-galactopyranose with the anhydro sugar 2 in the presence of N-iodosuccinimide did not give the expected iodoglycoside mixture, but instead gave an unusual 1,4:3,6-dianhydride 7 as the major product.
authors.affiliation: Department of Chemistry & Biochemistry, Seton Hall University, 400 South Orange Ave, South Orange, NJ, USA.
authors.forename: Vikram
authors.initials: V
authors.lastname: Basava
authors.affiliation: Department of Chemistry & Biochemistry, Seton Hall University, 400 South Orange Ave, South Orange, NJ, USA.
authors.forename: Sergiu M
authors.initials: SM
authors.lastname: Gorun
authors.affiliation: Department of Chemistry & Biochemistry, Seton Hall University, 400 South Orange Ave, South Orange, NJ, USA. Electronic address: cecilia.marzabadi@shu.edu.
authors.forename: Cecilia H
authors.initials: CH
authors.lastname: Marzabadi
mesh_terms: D003847:Deoxyglucose / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation
chemical_list: C001289:d-glucal; D003847:Deoxyglucose
keywords: 3, 6-Anhydro-d-glucal; 6-O-Tosyl-d-glucal; Addition reactions; Dianhydride sugar