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Total biosynthesis of harzianopyridone (65) and atpenin B (66). (A) Organization and predicted gene functions of the har and apn BGCs. Black ORFs encode for enzymes involved in the biosynthesis of 65 and 66 in the har and apn BGCs, respectively. (B) Proposed biosynthesis of 65. (C) Proposed mechanism of ring expansion and phenyl cleavage for the formation of 72 via radical intermediates.
