Attachment of oligosaccharides to proteins is a major post-translational modification. Chemical syntheses of oligosaccharides have contributed to clarifying the functions of these oligosaccharides. However, syntheses of oligosaccharide-linked proteins are still challenging because of their inherent complicated structures, including diverse di- to tetra-antennary forms. We report a highly efficient strategy to access the representative two types of triantennary oligosaccharides through only 9- or 10-step chemical conversions from a biantennary oligosaccharide, which can be isolated in exceptionally homogeneous form from egg yolk. Four benzylidene acetals were successfully introduced to the terminal two galactosides and two core mannosides of the biantennary asialononasaccharide bearing 24 hydroxy groups, followed by protection of the remaining hydroxy groups with acetyl groups. Selective removal of one of the benzylidene acetals gave two types of suitably protected glycosyl acceptors. Glycosylation toward the individual acceptors with protected Gal-β-1,4-GlcN thioglycoside and subsequent deprotection steps successfully yielded two types of complex-type triantennary oligosaccharides.

Oligosaccharides linked to proteins are known to play important roles in several biological events. However, oligosaccharides are heterogeneous, which has hindered detailed elucidation of oligosaccharide functions. In order to solve this problem, glycoproteins having homogeneous oligosaccharides have long been required. For this purpose, an effi cient preparative method of complex-type oligosaccharides has been investigated from a natural source and this method was found to afford over 24 kinds of diverse complex-type oligosaccharides by use of chemical methods and branch-specifi c sequential glycosidase digestion. The suffi cient amount of homogeneous complex type oligosaccharides obtained enabled us to examine the synthesis of homogeneous glycopeptides as well as glycoproteins by use of solid phase glycopeptide synthetic method and native chemical ligation. This review describes recent progress related to the effi cient method of oligosaccharide preparation and synthesis of glycoproteins including bioactive erythropoietin.

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