Labeling Studies Clarify the Committed Step in Bacterial Gibberellin Biosynthesis
Bacteria have evolved gibberellin phytohormone biosynthesis independently of plants and fungi. Through 13C-labeling and NMR analysis, the mechanistically unusual “B” ring contraction catalyzed by a cytochrome P450 (CYP114), which is the committed step in gibberellin biosynthesis, was shown to occur via oxidative extrusion of carbon-7 from ent-kaurenoic acid in bacteria. This is identical to the convergently evolved chemical transformation in plants and fungi, suggesting a common semipinacol rearrangement mechanism potentially guided by carbon-4α carboxylate proximity.
Reprinted (adapted) with permission from Labeling Studies Clarify the Committed Step in Bacterial Gibberellin Biosynthesis. Ryan S. Nett, Jeroen S. Dickschat, and Reuben J. Peters. Organic Letters 2016 18 (23), 5974-5977. DOI: 10.1021/acs.orglett.6b02569. Copyright 2016 American Chemical Society.