3.2 Glycosyl
Trichloroacetimidates
Richard R. Schmidt* 1 , Xiangming Zhu 2
1 Fachbereich Chemie, Fach M 725, Universität Konstanz,
78457 Konstanz, Germany
2 School of Chemistry and Chemical Biology, University College Dublin,
Belfield, Dublin 4, Ireland
richard.schmidt@uni-konstanz.de, xiangming@ucd.ie
1
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 452
2
Glycosyl Donor Generation Through Anomeric-Oxygen Exchange Reactions 453
3
Direct Anomeric Oxygen Alkylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 453
4
Glycosyl Donor Generation Through Retention of the Anomeric Oxygen . . . . 455
4.1
Methodological Aspects. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 460
4.2
Glycoside Synthesis on Polymer Supports . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 469
5
Recent Applications of O-Glycosyl Trichloroacetimidates
in Complex Oligosaccharide and GlycoconjugateSynthesis . . . . . . . . . . . . . . . . . . 482
5.1
Glycolipids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 482
5.2
Glycosyl Amino Acids and Glycopeptides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 488
5.3
Nucleoside and Nucleotide Glycosidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 493
5.4
Synthesis of Glycosaminoglycans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 493
5.5
Cell Wall Constituents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 498
5.6
Synthesis of Glycosylphosphatidyl Inositol Anchors . . . . . . . . . . . . . . . . . . . . . . . . . . . . 505
5.7
Glycosylation of Various Natural Products and Their Metabolites . . . . . . . . . . . . . . . 510
5.8
Cyclooligosaccharides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 514
5.9
C-Glycoside Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 514
5.10 O-Glycosyl Trichloroacetimidates of N,O- and S,O-Halfacetals . . . . . . . . . . . . . . . . . 515
6
Related Activation Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 516
7
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 517
Abstract
In the first part of this review, the basic principles of chemical glycosylation reactions are
discussed; this way the advantages of O-glycosyl trichloroacetimidates and related systems
as glycosyl donors become obvious. Many new methods for the generation of O-glycosyl
trichloroacetimidates and for their use as glycosyl donors have been introduced which are
In: Glycoscience. Fraser-Reid B, Tatsuta K, Thiem J (eds)
Chapter-DOI 10-1007/978-3-540-30429-6_11: © Springer-Verlag Berlin Heidelberg 2008