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Formation of eight-membered ring β-keto lactones via the intramolecular trapping of hydroxy acylketenes

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Abstract

Eight-membered ring β-keto lactones were prepared from 2,2,6-trimethyl-4H-1,3-dioxin-4-one in three steps involving conjugate addition to α,β-unsaturated aldehydes or ketones, followed by conversion to an alcohol and thermolysis. The formation of these eight-membered rings involves the intramolecular trapping of a hydroxy acyl ketene intermediate and is facilitated by a suppressed ring strain and an unfavorable intramolecular hydrogen bond, which is suggested to favor the formation of oligomers. These aspects of the reaction were supported by molecular mechanics calculations.

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Author notes

  1. Michael A. Patane

    Present address: Department of Medicinal Chemistry, Merck Research Laboratories, 19486, West Point, PA

Authors and Affiliations

  1. Department of Chemistry and Loker Hydrocarbon Research Institute, University of Southern California, 90089-1661, Los Angeles, CA, U.S.A.

    Nicos A. Petasis & Michael A. Patane

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  1. Nicos A. Petasis
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  2. Michael A. Patane
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Dedicated to Professor George A. Olah in honour of his many fundamental contributions to Chemistry recognized with the 1994 Nobel Prize.

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Petasis, N.A., Patane, M.A. Formation of eight-membered ring β-keto lactones via the intramolecular trapping of hydroxy acylketenes. Res. Chem. Intermed. 22, 781–790 (1996). https://doi.org/10.1163/156856796X00476

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  • DOI: https://doi.org/10.1163/156856796X00476

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