Photooxygenation of a microbial arene oxidation product and regioselective Kornblum-DeLamare rearrangement: Total synthesis of zeylenols and zeylenones

Matthew J Palframan, Gabriele Kociok-Kohn, Simon E Lewis

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52 Citations (Scopus)

Abstract

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).
Original languageEnglish
Pages (from-to)4766-4774
Number of pages9
JournalChemistry - A European Journal
Volume18
Issue number15
Early online date29 Feb 2012
DOIs
Publication statusPublished - 10 Apr 2012

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Regioselectivity
Oxidation
Benzoic Acid
Biological Products
Acids
zeylenone
zeylenol
cyclohexene
3-O-debenzoylzeylenone

Cite this

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abstract = "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).",
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T1 - Photooxygenation of a microbial arene oxidation product and regioselective Kornblum-DeLamare rearrangement: Total synthesis of zeylenols and zeylenones

AU - Palframan, Matthew J

AU - Kociok-Kohn, Gabriele

AU - Lewis, Simon E

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