2.6 C=C Bond Formation
Sławomir Jarosz, Marcin Nowogródzki
Institute of Organic Chemistry, Polish Academy of Sciences,
01–224 Warsaw, Poland
sljar@icho.edu.pl
1
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 344
2
General Methods of the Formation of the Double Bond . . . . . . . . . . . . . . . . . . . . . . . 346
3
Monosaccharides with the Endocyclic Double Bond . . . . . . . . . . . . . . . . . . . . . . . . . . 350
3.1 2,3-Unsaturated Monosaccharides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 350
3.2 3,4-Unsaturated Monosaccharides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 352
3.3 4,5-Unsaturated Monosaccharides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353
3.4 Rearrangement Reactions of Unsaturated Sugars . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 354
4
Monosaccharides with the Exocyclic Double Bond(s) . . . . . . . . . . . . . . . . . . . . . . . . . 358
4.1 5,6-Unsaturated Pyranosides (and 4,5-Unsaturated Furanosides) . . . . . . . . . . . . . . . . . . 361
5
Acyclic Unsaturated Sugars . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363
6
Application of Unsaturated Sugars as Chirons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 366
7
Miscellaneous . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 370
8
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 372
Abstract
The material presented in this chapter describes the general methodology used for the preparation of unsaturated sugars. The ‘older’ methods (i. e. those being developed since at least the
1950s) which are still very useful and have general application are also presented but they are
illustrated by newer examples. The direct formation of the double bond(s) is emphasized, but
the methodology based on the rearrangement of unsaturated sugars into other olefinic carbohydrates is also reviewed.
The emphasis is placed on the general methods rather than synthesis of individuals, since this
should give the reader a general view of the importance of unsaturated sugars and their application to stereocontrolled organic synthesis. All main classes of unsaturated sugars are described
briefly. The anomeric unsaturated derivatives are excluded from this review unless they serve
as starting materials in the preparation of other unsaturated carbohydrates via rearrangement
reactions.
Keywords
Synthesis; Rearrangement; Unsaturated sugars; Sugar chirons; Targeted synthesis
In: Glycoscience. Fraser-Reid B, Tatsuta K, Thiem J (eds)
Chapter-DOI 10-1007/978-3-540-30429-6_8: © Springer-Verlag Berlin Heidelberg 2008
Sławomir Jarosz, Marcin Nowogródzki
Institute of Organic Chemistry, Polish Academy of Sciences,
01–224 Warsaw, Poland
sljar@icho.edu.pl
1
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 344
2
General Methods of the Formation of the Double Bond . . . . . . . . . . . . . . . . . . . . . . . 346
3
Monosaccharides with the Endocyclic Double Bond . . . . . . . . . . . . . . . . . . . . . . . . . . 350
3.1 2,3-Unsaturated Monosaccharides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 350
3.2 3,4-Unsaturated Monosaccharides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 352
3.3 4,5-Unsaturated Monosaccharides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353
3.4 Rearrangement Reactions of Unsaturated Sugars . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 354
4
Monosaccharides with the Exocyclic Double Bond(s) . . . . . . . . . . . . . . . . . . . . . . . . . 358
4.1 5,6-Unsaturated Pyranosides (and 4,5-Unsaturated Furanosides) . . . . . . . . . . . . . . . . . . 361
5
Acyclic Unsaturated Sugars . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363
6
Application of Unsaturated Sugars as Chirons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 366
7
Miscellaneous . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 370
8
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 372
Abstract
The material presented in this chapter describes the general methodology used for the preparation of unsaturated sugars. The ‘older’ methods (i. e. those being developed since at least the
1950s) which are still very useful and have general application are also presented but they are
illustrated by newer examples. The direct formation of the double bond(s) is emphasized, but
the methodology based on the rearrangement of unsaturated sugars into other olefinic carbohydrates is also reviewed.
The emphasis is placed on the general methods rather than synthesis of individuals, since this
should give the reader a general view of the importance of unsaturated sugars and their application to stereocontrolled organic synthesis. All main classes of unsaturated sugars are described
briefly. The anomeric unsaturated derivatives are excluded from this review unless they serve
as starting materials in the preparation of other unsaturated carbohydrates via rearrangement
reactions.
Keywords
Synthesis; Rearrangement; Unsaturated sugars; Sugar chirons; Targeted synthesis
In: Glycoscience. Fraser-Reid B, Tatsuta K, Thiem J (eds)
Chapter-DOI 10-1007/978-3-540-30429-6_8: © Springer-Verlag Berlin Heidelberg 2008