When anomeric effects collide

  1. Christopher J. Cramer1,*,
  2. Anne-Marie Kelterer2,
  3. Alfred D. French3

Article first published online: 5 JUN 2001

DOI: 10.1002/jcc.1077

Issue

Journal of Computational Chemistry

Journal of Computational Chemistry

Volume 22, Issue 11, pages 1194–1204, August 2001

Additional Information

How to Cite

Cramer, C. J., Kelterer, A.-M. and French, A. D. (2001), When anomeric effects collide. Journal of Computational Chemistry, 22: 1194–1204. doi: 10.1002/jcc.1077

Author Information

  1. 1

    Department of Chemistry and Supercomputer Institute, University of Minnesota, 207 Pleasant St. SE, Minneapolis, Minnesota 55455-0431

  2. 2

    Institut für Physikalische und Theoretische Chemie, Technische Universität Graz, Technikerstrasse 4, A-8010 Graz, Austria

  3. 3

    United States Department of Agriculture, Agricultural Research Service, 1100 Robert E. Lee Blvd., P.O. Box 19687, New Orleans, Louisiana 70179-0687

*Department of Chemistry and Supercomputer Institute, University of Minnesota, 207 Pleasant St. SE, Minneapolis, Minnesota 55455-0431

Publication History

  1. Issue published online: 5 JUN 2001
  2. Article first published online: 5 JUN 2001
  3. Manuscript Accepted: 9 FEB 2001
  4. Manuscript Received: 21 DEC 2000

Funded by

  • the Alfred P. Sloan and John Simon Guggenheim Foundations
  • the Spanish Ministry of Education and Culture, and Fundación BBV

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Keywords:

  • anomeric effects;
  • rotational coordinates;
  • hyperconjugation;
  • polyethers

Abstract

Rotational coordinates about the C(3)–O(4) bonds of 2,4-dioxaheptane (DOH) and 2,4,6-trioxaheptane (TOH) are compared at correlated levels of electronic structure theory for gauche and trans orientations of the O(2)–C(3) bonds. TOH has overlapping anomeric effects, while DOH does not. The overlapping stereoelectronic effect shows its largest impact on the length of the O(2)–C(3) bond, which is typically 0.02 Å longer in DOH than in TOH. However, the energetic consequences of the overlapping anomeric effect in TOH are very small, as judged by total conformational energies and analysis of delocalization energies within a natural bond orbital framework. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1194–1204, 2001

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