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Synlett 2003(9): 1225-1240
DOI: 10.1055/s-2003-40349
ACCOUNT
© Georg Thieme Verlag Stuttgart ˙ New York

Stereoselective Chemical 1,2-cis O-Glycosylation: From ‘Sugar Ray’ to Modern Techniques of the 21st Century

Alexei V. Demchenko*
Department of Chemistry and Biochemistry, University of Missouri - St. Louis, 8001 Natural Bridge Rd., St. Louis, MO 63121, USA
Fax: +1(314)5165342; e-Mail: demchenkoa@umsl.edu;
Further Information

Publication History

Received 15 April 2003
Publication Date:
30 June 2003 (online)

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Abstract

The aim of this account is to discuss the accomplishments made in the area of the stereoselective O-glycosidic bond formation. Particularly, the account is focused on glycosylation methods for the synthesis of 1,2-cis glycosides.

1 Introduction

2 Historical Development

3 Anomeric Effect

4 Mechanistic Considerations

5 Factors Influencing the Stereoselectivity of Glycosylation

6 Anomeric Halides as Glycosyl Donors

6.1 Chlorides, Bromides, and Iodides

6.2 Fluorides

7 1-O Derivatives as Glycosyl Donors

7.1 Hemiacetals

7.2 O-Acyl, O-Carbonyl and Related Compounds

7.3 O-Imidates

7.4 Phosphites, Phosphates and Other O-P Derivatives

7.5 O-Sulfonyl Derivatives

7.6 Anomeric Transglycosylation

8 1-S Derivatives as Glycosyl Donors

8.1 Thioalkyl and Thioaryl Glycosides

8.2 2-Thiopyridyl and Related Cyclic 2-Thioimidates

8.3 Sulfoxides, Sulfimides, and Sulfones

8.4 Xanthates and Related Derivatives

8.5 Thiocyanates and Other Thio Derivatives

9 Miscellaneous and Indirect Methods

9.1 Miscellaneous Glycosyl Donors

9.2 Indirect Approaches

10 Conclusion

Key words

carbohydrates - new methods - glycosylation - oligo­saccharides - stereoselective synthesis - glycoconjugates