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Free, publicly-accessible full text available March 1, 2026
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The expanding world of biosynthetic pericyclases: cooperation of experiment and theory for discoveryCovering: 2000 to 2018 Pericyclic reactions are a distinct class of reactions that have wide synthetic utility. Before the recent discoveries described in this review, enzyme-catalyzed pericyclic reactions were not widely known to be involved in biosynthesis. This situation is changing rapidly. We define the scope of pericyclic reactions, give a historical account of their discoveries as biosynthetic reactions, and provide evidence that there are many enzymes in nature that catalyze pericyclic reactions. These enzymes, the “pericyclases,” are the subject of this review.more » « less
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Abstract We uncovered and reconstituted a concise biosynthetic pathway of the strained dipeptide (+)‐azonazine A from marine‐derivedAspergillus insulicola. Formation of the hexacyclic benzofuranoindoline ring system from cyclo‐(l‐Trp‐N‐methyl‐l‐Tyr) is catalyzed by a P450 enzyme through an oxidative cyclization. Supplementing the producing strain with various indole‐substituted tryptophan derivatives resulted in the generation of a series of azonazine A analogs.more » « less
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