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Facial Selectivity in the Diels–Alder Reactions of 2,2-Disubstituted Cyclopent-4-ene-1,3-dione Derivatives and a Computational Examination of the Facial Selectivity of the Diels–Alder Reactions of Structurally Related Dienes and Dienophiles

  1. Pei-Ying Liu1,
  2. Yong-Jin Wu1,
  3. Cory C. Pye2,
  4. Paul D. Thornton3,
  5. Raymond A. Poirier1,
  6. D. Jean Burnell1,3

Article first published online: 28 DEC 2011

DOI: 10.1002/ejoc.201101301

Issue

European Journal of Organic Chemistry

European Journal of Organic Chemistry

Volume 2012, Issue 6, pages 1186–1194, February 2012

Additional Information

How to Cite

Liu, P.-Y., Wu, Y.-J., Pye, C. C., Thornton, P. D., Poirier, R. A. and Burnell, D. J. (2012), Facial Selectivity in the Diels–Alder Reactions of 2,2-Disubstituted Cyclopent-4-ene-1,3-dione Derivatives and a Computational Examination of the Facial Selectivity of the Diels–Alder Reactions of Structurally Related Dienes and Dienophiles. Eur. J. Org. Chem., 2012: 1186–1194. doi: 10.1002/ejoc.201101301

Author Information

  1. 1

    Department of Chemistry, Memorial University of Newfoundland, St. John's, Newfoundland and Labrador, A1B 3X7 Canada

  2. 2

    Department of Chemistry, St. Mary's University, Halifax, Nova Scotia, B3H 3C3 Canada

  3. 3

    Department of Chemistry, Dalhousie University, P. O. Box 15000, Halifax, Nova Scotia, B3H 4R2 Canada, Fax: +1-902-494-1310

Publication History

  1. Issue published online: 13 FEB 2012
  2. Article first published online: 28 DEC 2011
  3. Manuscript Received: 7 SEP 2011

Funded by

  • Natural Sciences and Engineering Research Council of Canada

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Keywords:

  • Cycloaddition;
  • Density functional calculations;
  • Diastereoselectivity;
  • Steric hindrance

Abstract

The facial selectivity in the Diels–Alder reactions via endo transition states of the plane-nonsymmetric dienophiles spiro[bicyclo[2.2.2]octane-2,1′-[3]cyclopentene]-2′,5′-dione (6) and spiro[bicyclo[2.2.1]heptane-2,1′-[3]cyclopentene]-2′,5′-dione (7) has been found to be very similar to the facial selectivity of reactions of cyclopentadienes fused to bicyclo[2.2.2]octane and bicyclo[2.2.1]heptane (4 and 5). This is strong evidence for steric control in their facial selectivities. Density functional computations involving the reactions of these compounds, as well as a series of conformationally locked model addends (26a–c and 27a–c), revealed geometrical and energetic properties that confirmed that the facial selectivity is governed by steric effects. Steric interactions appeared to be the reason for the low endo/exo selectivity of dienophiles 6, 7, 2,2-dimethylcyclopent-4-ene-1,3-dione (20), and spiro[5.4]dec-8-ene-7,10-dione (23).

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