Total Synthesis of Complex Biosynthetic Late-Stage Intermediates and Bioconversion by a Tailoring Enzyme from
Frederick Lindner1, Steffen Friedrich1, Frank Hahn1
1Professur für Organische Chemie (Lebensmittelchemie), Department of Chemistry, Fakultät für Biologie, Chemie und Geowissenschaften , Universität Bayreuth , Universitätsstraße 30 , 95447 Bayreuth , Germany.
Abstract:
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.
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