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Oligosaccharide Trans-Glycoside ³J_COCC Karplus Curves Are Not Equivalent: Effect of Internal Electronegative Substituents

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Hongqiu Zhao,^† Ian Carmichael,^‡ and Anthony S. Serianni*^†

Department of Chemistry and Biochemistry and the Radiation Laboratory, University of Notre Dame, Notre Dame, Indiana 46556-5670 aseriann@nd.edu

J. Org. Chem., 2008, 73 (8), pp 3255–3257

DOI: 10.1021/jo702288h

Publication Date (Web): March 20, 2008

†

Department of Chemistry and Biochemistry.

‡

Radiation Laboratory.

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

Abstract

Density functional theory (DFT) calculations show that internal electronegative substituents perturb ³J_COCC Karplus curves by phase shifting them with respect to analogous pathways devoid of this substitution. Thus, the J-coupling maximum, which normally is observed near 180°, is shifted by 15°. These findings suggest that the two types of inter-residue C−O−C−C coupling pathways observed in many oligosaccharides cannot be treated using a generalized ³J_COCC Karplus equation. Quantitative interpretations of trans-glycoside J-couplings to evaluate linkage conformations will need to take this effect into account.

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Published In Issue April 18, 2008
Received October 23, 2007

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Oligosaccharide Trans-Glycoside ³J_COCC Karplus Curves Are Not Equivalent: Effect of Internal Electronegative Substituents