ortho-Methylphenylthioglycosides as glycosyl building blocks for preactivation-based oligosaccharide synthesis

• Published in: Carbohydrate research Vol. 384; pp. 1 - 8
• Main Authors: Peng, Peng, Xiong, De-Cai, Ye, Xin-Shan
• Format: Journal Article
• Language: English
• Published: Netherlands Elsevier Ltd 30-01-2014
• Subjects: Aglycon transfer; Glycosylation; Molecular Structure; o-Methylphenylthioglycoside; Oligosaccharide; Oligosaccharides - chemical synthesis; Oligosaccharides - chemistry; Preactivation; Thioglycosides - chemistry; Toluene - analogs & derivatives; Toluene - chemistry; Glycosylation; o-Methylphenylthioglycoside; Preactivation; Aglycon transfer; Oligosaccharide
• ISSN: 0008-6215; 1873-426X
• DOI: 10.1016/j.carres.2013.11.009

•o-Methylphenylthioglycosides were used as blocks in preactivation protocol.•The aglycon transfer was avoided.•The efficiency of glycosyl coupling reactions was enhanced.•The thioglycosides were efficiently employed in one-pot oligosaccharide assembly.
Thioglycosides are widely used in orthogonal glycosylation, armed-disarmed chemoselective glycosylation, and preactivation-based glycosylation. Nevertheless, aglycon transfer occasionally occurred in the glycosylation process of thioglycosides. This problem was also encountered in preactivation-based reactions, which limited the applications of preactivation-based glycosylation to some extent. To tackle this problem, sterically hindered aglycon ortho-methylphenylthioglycosides were introduced as glycosyl building blocks. These thioglycosides prevented the aglycon transfer and enhanced the efficiency of glycosyl coupling reactions, especially in the reactions of disarmed donors with armed acceptors. Moreover, these thioglycosides were employed in preactivation-based one-pot oligosaccharide assembly.