Total Synthesis of Complex Biosynthetic Late-Stage Intermediates and Bioconversion by a Tailoring Enzyme from Jerangolid Biosynthesis

A highly convergent access to the late-stage biosynthetic intermediates projerangolid and jerangolid E is presented, and its utility is demonstrated by the synthesis of novel non-natural jerangolid derivatives. The key steps are fragment couplings by Julia–Kocienski olefination and olefin cross meta...

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Bibliographic Details
Published in:Journal of organic chemistry 2018-11, Vol.83 (22), p.14091-14101
Main Authors: Lindner, Frederick, Friedrich, Steffen, Hahn, Frank
Format: Article
Language:English
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Summary:A highly convergent access to the late-stage biosynthetic intermediates projerangolid and jerangolid E is presented, and its utility is demonstrated by the synthesis of novel non-natural jerangolid derivatives. The key steps are fragment couplings by Julia–Kocienski olefination and olefin cross metathesis, as well as a stereoselective tetrahydropyran formation by intramolecular oxa-Michael addition. Bioconversion experiments with the tailoring O-methyltransferase JerF confirmed its proposed biosynthetic role and revealed relaxed substrate specificity of this enzyme as well as tolerance to organic cosolvents.
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.8b02047