Microwave-Assisted One-Pot Synthesis of 1,6-Anhydrosugars and Orthogonally Protected Thioglycosides

Living organisms employ glycans as recognition elements because of their large structural information density. Well-defined sugar structures are needed to fully understand and take advantage of glycan functions, but sufficient quantities of these compounds cannot be readily obtained from natural sou...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2014-10, Vol.136 (41), p.14425-14431
Main Authors: Ko, Yen-Chun, Tsai, Cheng-Fang, Wang, Cheng-Chung, Dhurandhare, Vijay M, Hu, Pu-Ling, Su, Ting-Yang, Lico, Larry S, Zulueta, Medel Manuel L, Hung, Shang-Cheng
Format: Article
Language:English
Subjects:
Carbohydrate Conformation
Microwaves
Oligosaccharides - chemical synthesis
Oligosaccharides - chemistry
Thioglycosides - chemical synthesis
Thioglycosides - chemistry
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Summary:Living organisms employ glycans as recognition elements because of their large structural information density. Well-defined sugar structures are needed to fully understand and take advantage of glycan functions, but sufficient quantities of these compounds cannot be readily obtained from natural sources and have to be synthesized. Among the bottlenecks in the chemical synthesis of complex glycans is the preparation of suitably protected monosaccharide building blocks. Thus, easy, rapid, and efficient methods for building-block acquisition are desirable. Herein, we describe routes directly starting from the free sugars toward notable monosaccharide derivatives through microwave-assisted one-pot synthesis. The procedure followed the in situ generation of per-O-trimethylsilylated monosaccharide intermediates, which provided 1,6-anhydrosugars or thioglycosides upon treatment with either trimethylsilyl trifluoromethanesulfonate or trimethyl­(4-methylphenylthio)­silane and ZnI2, respectively, under microwave irradiation. We successfully extended the methodology to regioselective protecting group installation and manipulation toward a number of thioglucosides and the glycosylation of persilylated derivatives, all of which were conducted in a single vessel. These developed approaches open the possibility for generating arrays of suitably protected building blocks for oligosaccharide assembly in a short period with minimal number of purification stages.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja504804v