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13C-13C NMR spin-spin coupling constants in saccharides: structural correlations involving all carbons in aldohexopyranosyl rings.

Bose-Basu B, Klepach T, Bondo G, Bondo PB, Zhang W, Carmichael I, Serianni AS

Department of Chemistry and Biochemistry and Radiation Laboratory, University of Notre Dame, Notre Dame, Indiana 46556, USA.

13C-13C Spin-spin coupling constants (JCC) have been measured in a group of aldohexopyranoses and methyl aldopyranosides singly labeled with 13C at different sites to confirm and extend prior correlations between JCC magnitude and sign and saccharide structure. Structural correlations for 2JC1,C3, 2JC2,C4, 2JC4,C6, and 2JC1,C5 have been confirmed using density functional theory calculations to test empirical predictions. These geminal couplings depend highly on the orientation of C-O bonds appended to the terminal coupled carbons, but new evidence suggests that 2JCCC values are also affected by intervening carbon structure and C-O bond rotation. 3JC1,C6 and 3JC3,C6 values show Karplus-like dependences but also are affected by in-plane terminal hydroxyl substituents. In both cases, rotation about the C5-C6 bond modulates the coupling due to the alternating in-plane and out-of-plane O6. 3JC3,C6 is also affected by C4 configuration. Both 3JC1,C6 and 3JC3,C6 are subject to remote effects involving the structure at C3 and C1, respectively. New structural correlations have been determined for 2JC3,C5, which, like 3JC3,C6, shows a remote dependence on anomeric configuration. Investigations of dual pathway 13C-13C couplings, 3+3JC1,C4 and 3+3JC2,C5, revealed an important additional internal electronegative substituent effect on 3JCC in saccharides, a structural factor undocumented previously and one of importance to the interpretation of trans-glycoside 3JCOCC in oligosaccharides.

Published 21 September 2007 in J Org Chem, 72(20): 7511-22.
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