Publisher Summary This chapter provides an overview of the 13 Carbon-nuclear magnetic resonance ( 13 C-NMR) spectroscopy of monosaccharides. The 13 C-NMR spectroscopy has become increasingly important as a tool for the characterization and structural elucidation of sugars and their derivatives. Although 13 C-NMR is closely related to 1 H-NMR spectroscopy, especially when both types of spectra are recorded with Fourier-transform instruments, the two techniques are sufficiently different to be valuable complements to each other. In many cases, in particular when dealing with complex molecules such as polysaccharides, the amount of information obtainable from 1 H-NMR spectra is limited as compared to that revealed by 13 C- NMR spectra. This chapter provides an almost complete collection of 13 C- NMR chemical shifts of monosaccharides, their methyl glycosides, and acetates, along with the examples of shift data for as many different types of monosaccharide derivative as possible. It also provides details on sampling techniques and assignment techniques, and discusses the identity of monosaccharides, their structure determination, and conformational analysis .

Carbon-13 Nuclear Magnetic Resonance Spectroscopy of Monosaccharides

Glycoproteins, glycolipids, and glycophospholipids (glycoconjugates) are components of membranes. The oligosaccharide residue is responsible for intercellular recognition and interaction; it acts as a receptor for proteins, hormones, and viruses and governs immune reactions. These significant activities have stimulated interest in oligosaccharides and glycoconjugates. With their help it should be possible to clarify the molecular basis of these phenomena and to derive new principles of physiological activity. Major advances in the synthesis of oligosaccharides have been made by the use of the Koenigs-Knorr method, in which glycosyl halides in the presence of heavy-metal salts are employed to transfer the glycosyl group to nucleophiles. The disadvantages of this procedure have led to an intensive search for new methods. Such methods will be discussed in this article. Emphasis is placed on glycoside and saccharide formation by 1-O-alkylation, on the trichloroacetimidate method, and on activation through the formation of glycosylsulfonium salts and glycosyl fluorides.

New Methods for the Synthesis of Glycosides and Oligosaccharides—Are There Alternatives to the Koenigs‐Knorr Method? [New Synthetic Methods (56)]

Traditionally, access to structurally defined complex carbohydrates has been very laborious Although recent advancements in solid-phase synthesis have made the construction of complex oligosaccharides less tedious, a high level of technical expertise is still necessary to obtain the desired structures We describe the automated chemical synthesis of several oligosaccharides on a solid-phase synthesizer A branched dodecasaccharide was synthesized through the use of glycosyl phosphate building blocks and an octenediol functionalized resin The target oligosaccharide was readily obtained after cleavage from the solid support Access to certain complex oligosaccharides now has become feasible in a fashion much like the construction of oligopeptides and oligonucleotides

http://science.sciencemag.org/content/sci/291/5508/1523.full.pdf

Automated Solid-Phase Synthesis of Oligosaccharides

Methods for Selective Modifications of Cyclodextrins.

Anomeric-oxygen activation for glycoside synthesis: the trichloroacetimidate method.

A novel promoter for the efficient construction of 1,2-trans linkages in glycoside synthesis, using thioglycosides as glycosyl donors

The methylated analogues of s-cyclodextrin dissolve in cold water 10 – 20 times better than s-cyclodextrin itself, however, quite unusually on heating they crystallize from the solution. The structure of heptakis-(2,6-di-O-methyl)- and heptakis-(2,3,6-tri-O-methyl)-s-cyclodextrin was proved by gas-liquid chromatographic and 1H-NMR and 13C-NMR spectroscopic investigations. The corresponding model compounds were synthetized and, according to 13C-NMR spectroscopic investigations, a part of the so far published NMR assignations have to be corrected.

Péter Fügedi

Papers

A novel promoter for the efficient construction of 1,2-trans linkages in glycoside synthesis, using thioglycosides as glycosyl donors

Synthesis and 13C‐NMR Spectroscopy of Methylated beta‐Cyclodextrins

Synthesis of heptakis(6-O-tert-butyldimethylsilyl)cyclomaltoheptaose and octakis(6-O-tert-butyldimethylsilyl)cyclomalto-octaose

Synthesis of 1,2-cis-linked glycosides using dimethyl(methylthio)sulfonium triflate as promoter and thioglycosides as glycosyl donors

Syntheses of a branched heptasaccharide having phytoalexin-elicitor activity