3.7 Anomeric Anhydro Sugars
Nathan W. McGill, Spencer J. Williams*
School of Chemistry, The University of Melbourne,
Parkville, VIC 3052, Australia
n.mcgill@pgrad.unimelb.edu.au, sjwill@unimelb.edu.au
1
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 738
1.1 General Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 738
2
1,6-Anhydrohexopyranoses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 738
2.1 Occurrence and Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 738
2.2 Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 742
2.3 Cleavage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 744
3
1,2-Anhydro Sugars. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 745
4
Miscellaneous Anhydro Sugars . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 747
4.1 1,3-Anhydro Sugars . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 747
4.2 1,4-Anhydropyranoses (1,5-Anhydrofuranoses) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 748
4.3 1,6-Anhydrohexofuranoses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 748
4.4 Levoglucosenone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 749
5
Anhydro Sugars Containing Nitrogen, Sulfur, or Selenium . . . . . . . . . . . . . . . . . . . . 750
Abstract
Anomeric anhydro sugars are sugar derivatives where the anomeric carbon participates in an
acetal linkage with two of the hydroxyl groups of the sugar. They are essentially intramolecular glycosides, and their bicyclic nature provides a powerful conformational constraint that
greatly influences their reactivity. This chapter reviews the occurrence, properties, formation,
and reactions of anomeric anhydro sugars. Particular emphasis is placed on 1,2- and 1,6-anhydropyranoses, including conformational aspects and ring-opening reactions. Epoxide-containing 1,6-anhydro sugars ( ˇ
Cerný epoxides) are briefly reviewed, and the formation and some
reactions of the 1,6-anhydro sugar enone, levoglucosenone, is covered. An overview is given of the use of 1,2-anhydro sugar as glycosyl donors. Also discussed are the formation and
reactions of anomeric anhydro sugars containing nitrogen, sulfur, or selenium.
Keywords
Anhydro sugars; Dianhydro sugars; Epoxide; Glucosan; Glycosan; Levoglucosan;
Levoglucosenone; Seleno sugar; Selenolevoglucosan; Thiolevoglucosan
Abbreviations
CSA
camphorsulfonic acid
DMDO 3,3-dimethyldioxirane
In: Glycoscience. Fraser-Reid B, Tatsuta K, Thiem J (eds)
Chapter-DOI 10-1007/978-3-540-30429-6_16: © Springer-Verlag Berlin Heidelberg 2008