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Morgan KM, Gronert S. Structural and solvent effects on the mechanism of base-induced rearrangement of epoxides to allylic alcohols. J Org Chem. 2000;65(5):1461-6doi: 10.1021/jo991619q.
Morgan, K. M., & Gronert, S. (2000). Structural and solvent effects on the mechanism of base-induced rearrangement of epoxides to allylic alcohols. The Journal of organic chemistry, 65(5), 1461-6. https://doi.org/10.1021/jo991619q
Morgan, and Gronert. "Structural and solvent effects on the mechanism of base-induced rearrangement of epoxides to allylic alcohols." The Journal of organic chemistry vol. 65,5 (2000): 1461-6. doi: https://doi.org/10.1021/jo991619q
Morgan KM, Gronert S. Structural and solvent effects on the mechanism of base-induced rearrangement of epoxides to allylic alcohols. J Org Chem. 2000 Mar 10;65(5):1461-6. doi: 10.1021/jo991619q. PMID: 10814110.
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J Org Chem. 2000 Mar 10;65(5):1461-6. doi: 10.1021/jo991619q.

Structural and solvent effects on the mechanism of base-induced rearrangement of epoxides to allylic alcohols.

The Journal of organic chemistry

Morgan, Gronert

Affiliations

  1. Department of Chemistry, College of William & Mary, P.O. Box 8795, Williamsburg, Virginia 23187, and Department of Chemistry and Biochemistry, San Francisco State University, San Francisco, California 94132, USA.

PMID: 10814110 DOI: 10.1021/jo991619q

Abstract

A combined experimental and computational study is presented which explores the influence of structure and solvent on the base-catalyzed isomerization of cyclopentene- and cyclohexene oxides. Cyclohexene oxide is known to rearrange via a syn beta-elimination in nonpolar solvents. Cyclopentene oxide instead undergoes alpha-elimination to a carbenoid intermediate in nonpolar solvents due to the unusual acidity of the alpha-proton, not because of an unfavorable conformation. In HMPA, cyclopentene oxide undergoes beta-elimination. To explore the origins of this mechanistic change, deuterium-labeled cis-4-tert-butylcyclohexene oxide was rearranged in HMPA and was found to react via anti beta-elimination, as presumably do cyclopentene oxide and other epoxides.

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