Functionally Distinct Modules Operate Two Consecutive α,β→β,γ Double‐Bond Shifts in the Rhizoxin Polyketide Assembly Line

Abstract

Shift work: Biochemical analysis of the rhizoxin pathway revealed that the diene moiety is not shifted all at once, but through distinct enzymatic operations. The first shift occurs by a formal β,γ-dehydration in module 7, while the second double bond is first generated by module 8 and then shifted by an unprecedented “shift module” with a novel type of DH* domain (see scheme). ACP=acyl carrier protein, DH*=dehydratase-like shift domain. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.