Oxidative Ring Cleavage in Jadomycin Biosynthesis: A Multistep Oxygenation Cascade in a Biosynthetic Black Box

Backbone‐breaking oxygenase clusters. Inactivation of the oxygenase‐encoding genes jadH and jadG and structure elucidation of novel accumulation products illustrate the essential interactions within the biosynthetic protein complex that govern the oxygenation cascade leading to the cleavage of the angucycline backbone during jadomycin biosynthesis by Streptomyces venezuelae. These results also allow the elucidation of the dehydration sequence (shown) that yields the aromatic ring A of the jadomycin scaffold.