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Synthetic chain terminators were used to capture the biosynthetic intermediates from a partially reducing iterative type I polyketide synthase, which is integrated into a multimodular biosynthesis enzyme. The off-loaded metabolites clarified the timing of ketoreduction and aromatization in the assembly of the antibiotic micacocidin.

Graphical abstract: Chemical chain termination resolves the timing of ketoreduction in a partially reducing iterative type I polyketide synthase

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