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Characterization of the role and extent of pericyclic reactions in natural product biosynthetic pathways has dramatically increased over the past decade. By definition, pericyclic transformations involve the concerted conversion of a substrate to product without any detectable intermediates. Examples of four major types: electrocyclizations (e.g. 7-dehydrocholesterol to pre-vitamin D3), cycloadditions (e.g. Diels–Alder [4+2]-cyclizations in conversion of trienes to decalins), sigmatropic shifts (e.g. Cope rearrangements), and Alder-ene reactions have been validated to occur in biologic systems. Diels–Alderases have been found to catalyze intramolecular decalin formations and spiro-tetronate/spiro-tetramate cyclizations, as well as intermolecular cyclizations. Pericyclase-catalyzed heteroatom cyclizations include pyridine ring formation in thiazole-containing nonribosomal thiazolopeptide antibiotics. In the biosynthetic route to the vinca anticancer alkaloids vinblastine and vincristine, a metabolic precursor stemmadenine has been shown to undergo variants of enzyme-catalyzed [4+2]-cyclizations to give catharanthine and tabersonine frameworks.

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