Elucidation of ustilaginoidin biosynthesis reveals a previously unrecognised class of ene-reductases
Dan Xu, Ruya Yin, Zhiyao Zhou, Gan Gu, Siji Zhao, Jin‐Rong Xu, Junfeng Liu, You‐Liang Peng, Daowan Lai, Ligang Zhou
Abstract
dimerization of YWA1 (and 3-methyl YWA1) followed by dehydration was discovered. Intriguingly, the reduction of the 2,3-double bond of the pyrenone ring was catalyzed by a phospholipid methyltransferase-like enzyme (UsgR). The reductase was specific for reduction of monomeric, linear naphtho-γ-pyrenones, but not for the dimers. Atroposelective coupling of various monomers by the laccase (UsgL) led to diverse ustilaginoidins. Moreover, 3-epimerism of the 3-methyl-2,3-dihydro-naphtho-γ-pyrones adds additional complexity to the biosynthesis.
Topics & Concepts
Ene reactionBiosynthesisClass (philosophy)StereochemistryChemistryBiochemistryPhilosophyEnzymeEpistemologyPlant biochemistry and biosynthesisPhotosynthetic Processes and MechanismsMicrobial bioremediation and biosurfactants