NMR in Glycoscience and Glycotechnology
CHAPTER 2: NMR Spin-Couplings in Saccharides: Relationships Between Structure, Conformation and the Magnitudes of JHH, JCH and JCC Values
Published:15 May 2017
Special Collection: 2017 ebook collectionSeries: New Developments in NMR
M. J. Hadad, W. Zhang, T. Turney, L. Sernau, X. Wang, R. J. Woods, ... A. S. Serianni, in NMR in Glycoscience and Glycotechnology, ed. K. Kato and T. Peters, The Royal Society of Chemistry, 2017, pp. 20-100.
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NMR spin–spin coupling constants (scalar couplings, J-couplings) are highly abundant in saccharides, with multiple values often reporting on the same structural domain (redundancy). While conventional analyses of J-couplings typically involve studies of these parameters in relation to individual structural elements, future treatments are more likely to involve simultaneous analyses of large numbers of redundant (and in some cases correlated) J-couplings sensitive to multiple structural domains, providing a more complete appraisal of local molecular structure in solution. These analyses require quantitative relationships between J-couplings and saccharide structure. This chapter provides a detailed look at structural information encoded in one-bond (1J), two-bond (2J), three-bond (3J), four-bond (4J), and dual pathway (2+3J, 3+3J) scalar couplings involving hydrogen and carbon as coupled nuclei in saccharides. Experimental and computational data are integrated to illustrate correlations between saccharide structure, J-coupling magnitude and J-coupling sign. Topics ranging from selective isotopic labeling to enable J-coupling measurements, experimental methods to determine J-coupling magnitudes and signs, and the effects of specific types of molecular motions on the behaviors of saccharide J-couplings are treated. While work published over the past fifteen years comprise the main discussion, new data are included to augment or refine prior findings, notably on long-range 4JHH values in aldopyranosyl rings and across O-glycosidic linkages, and J-couplings pertinent to conformational analyses of glycosidic linkages.