title: Polyketide-chain branching by an enzymatic Michael addition.
abstract: A new "branch" for polyketide synthases was discovered in the biosynthesis of the antimitotic rhizoxin complex in the endofungal bacterium Burkholderia rhizoxinica. Genetic engineering and the structural elucidation of pathway intermediates revealed that a complex polyketide chain is branched at the beta position by an unprecedented conjugate addition of an acetyl building block to an acryloyl precursor (see scheme).
authors.affiliation: Leibniz Institute for Natural Product Research and Infection Biology, HKI, Department of Biomolecular Chemistry and Bio Pilot Plant, Beutenbergstrasse 11a, 07745 Jena, Germany.
authors.forename: Björn
authors.initials: B
authors.lastname: Kusebauch
authors.forename: Benjamin
authors.initials: B
authors.lastname: Busch
authors.forename: Kirstin
authors.initials: K
authors.lastname: Scherlach
authors.forename: Martin
authors.initials: M
authors.lastname: Roth
authors.forename: Christian
authors.initials: C
authors.lastname: Hertweck
mesh_terms: D000970:Antineoplastic Agents / Q000737:chemistry*; D055162:Biocatalysis; D019117:Burkholderia / Q000201:enzymology; D055786:Gene Knockout Techniques; D018942:Macrolides / Q000737:chemistry*; D005810:Multigene Family; D048630:Polyketide Synthases / Q000235:genetics / Q000378:metabolism*; D017434:Protein Structure, Tertiary
chemical_list: D000970:Antineoplastic Agents; D018942:Macrolides; D048630:Polyketide Synthases; C041443:rhizoxin