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We report the enantioselective total syntheses of zeylenol (+)-1, as well as its congeners (-)-7 and 16, and of 3-O-debenzoylzeylenone 28. To this end, a new variant of the Kornblum-DeLaMare rearrangement, which utilises neighbouring-group participation to impart regioselectivity, has been developed. The approach employs photooxygenation of building blocks derived from a microbial arene oxidation product. New light on a Korny rearrangement: Biooxidation of benzoic acid with R. eutrophus B9 gives a dearomatised diene diol acid that allows concise access to the zeylenol and zeylenone family of polyoxygenated cyclohexene natural products. The synthesis employs diene photooxygenation and a new regioselective variant of the Kornblum-DeLaMare endoperoxide fragmentation has been developed (see scheme).
Palframan, M. J., Kociok-Kohn, G., & Lewis, S. E. (2012). Photooxygenation of a microbial arene oxidation product and regioselective Kornblum-DeLamare rearrangement: Total synthesis of zeylenols and zeylenones. Chemistry - A European Journal, 18(15), 4766-4774. https://doi.org/10.1002/chem.201104035