Description:
<jats:title>Abstract</jats:title><jats:p>Myxalamids are potent inhibitors of the eukaryotic electron transport chain produced by different myxobacteria. Here, we describe the identification of the myxalamid biosynthesis gene cluster from <jats:italic>Myxococcus xanthus</jats:italic>. Additionally, new myxalamids (<jats:bold>5</jats:bold>–<jats:bold>13</jats:bold>) have been obtained by mutasynthesis from <jats:italic>bkd</jats:italic> mutants of <jats:italic>M. xanthus</jats:italic> and <jats:italic>Stigmatella aurantiaca</jats:italic>. Moreover, as these <jats:italic>bkd</jats:italic> mutants are still able to produce myxalamid B (<jats:bold>2</jats:bold>), the origin of the isobutyryl‐CoA (IB‐CoA) starter unit required for its biosynthesis has been determined. In a <jats:italic>M. xanthus bkd</jats:italic> mutant, IB‐CoA originates from valine, but in <jats:italic>S. aurantiaca</jats:italic> this starter unit is derived from α‐oxidation of iso‐odd fatty acids, thereby connecting primary and secondary metabolism.</jats:p>