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Substitution of a histidine, comprising part of the catalytic base group in the ent‐copalyl diphosphate synthases found in all seed plants for gibberellin phytohormone metabolism, by a larger aromatic residue leads to rearrangements. Through a series of 1,2‐hydride and methyl shifts of the initially formed bicycle predominant formation of (−)‐kolavenyl diphosphate is observed. Further mutational analysis...
An active‐site water molecule coordinated by conserved histidine and asparagine residues seems to serve as the catalytic base in all ent‐copalyl diphosphate synthases (CPSs). When these residues are substituted by alanine, the mutant CPSs produce stereochemically novel ent‐8‐hydroxy‐CPP. Given the requisite presence of CPSs in all land plants for gibberellin phytohormone biosynthesis, such plasticity...
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