Labeling Studies Clarify the Committed Step in Bacterial Gibberellin Biosynthesis

[Image: see text] Bacteria have evolved gibberellin phytohormone biosynthesis independently of plants and fungi. Through (13)C-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.