2.4 Anhydrosugars
Sławomir Jarosz, Marcin Nowogródzki
Institute of Organic Chemistry, Polish Academy of Sciences,
01–224 Warsaw, Poland
sljar@icho.edu.pl
1
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 272
2
Anomeric Anhydrosugars: Synthesis and Reactions . . . . . . . . . . . . . . . . . . . . . . . . . 274
2.1
1,6-Anhydrosugars . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 274
2.1.1 1,6-Anhydrohexopyranoses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 274
2.1.2 1,6-Anhydrofuranoses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 279
2.2
Higher Anhydroaldoses and Anhydroketoses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 279
2.3
1,2-Anhydrosugars . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 280
2.4
1,3- and 1,4-Anhydrosugars . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 283
3
Non-anomeric Anhydrosugars: Synthesis and Reactions . . . . . . . . . . . . . . . . . . . . 284
3.1
Sugar Oxiranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
3.1.1 2,3-Anhydrosugars . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
3.1.2 Exocyclic Epoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
3.1.3 Rearrangement of Sugar Epoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
3.2
Sugar Oxetanes, Oxolanes (THF), and THP Derivatives . . . . . . . . . . . . . . . . . . . . . . . . 292
4
Anhydronucleosides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 295
5
Miscellaneous . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 297
6
Conclusion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
Abstract
The anhydrosugars are reviewed in this chapter. The emphasis is placed on the general methodology of their preparation, as well as, their application in stereocontrolled organic synthesis.
The material is divided into two main parts: anomeric anhydrosugars and non-anomeric ones.
In the first class, 1,2-sugar epoxides and 1,6-anhydrosugars are the most important since they
offer significant synthetic potential in targeted synthesis of important compounds. From the
second class, sugar epoxides (2,3- and 3,4-oxiranes) are particularly useful. The synthesis of
both classes of anhydrosugars (anomeric and non-anomeric) is illustrated by selected examples
including older examples (i. e. those described also in the previous edition of this monograph)
and those published more recently. Various methods for the preparation of anhydrosugars are
described in order to give the reader a general impression of the importance of such derivatives
both as biologically active targets (illustrated by selected examples of anhydronucleosides)
and optically pure building blocks in targeted synthesis. The material included in this chapter
In: Glycoscience. Fraser-Reid B, Tatsuta K, Thiem J (eds)
Chapter-DOI 10-1007/978-3-540-30429-6_6: © Springer-Verlag Berlin Heidelberg 2008