3W8X

The complex structure of EncM with trifluorotriketide

3W8X の概要

• エントリーDOI: 10.2210/pdb3w8x/pdb
• 関連するPDBエントリー: 3W8W 3W8Y 3W8Z
• 分子名称: Putative FAD-dependent oxygenase EncM, FLAVIN-ADENINE DINUCLEOTIDE, 6,6,6-trifluoro-1-phenylhexane-1,3,5-trione, ... (5 entities in total)
• 機能のキーワード: monooxygenase, flavin binding, oxidoreductase
• 由来する生物種: Streptomyces maritimus
• タンパク質・核酸の鎖数: 2
• 化学式量合計: 103006.99

構造登録者

Teufel, R.,Miyanaga, A.,Stull, F.,Michaudel, Q.,Louie, G.,Noel, J.P.,Baran, P.S.,Palfey, B.,Moore, B.S. (登録日: 2013-03-22, 公開日: 2013-10-30, 最終更新日: 2023-11-08)

主引用文献

Teufel, R.,Miyanaga, A.,Michaudel, Q.,Stull, F.,Louie, G.,Noel, J.P.,Baran, P.S.,Palfey, B.,Moore, B.S.
Flavin-mediated dual oxidation controls an enzymatic Favorskii-type rearrangement.
Nature, 503:552-556, 2013

PubMed Abstract: Flavoproteins catalyse a diversity of fundamental redox reactions and are one of the most studied enzyme families. As monooxygenases, they are universally thought to control oxygenation by means of a peroxyflavin species that transfers a single atom of molecular oxygen to an organic substrate. Here we report that the bacterial flavoenzyme EncM catalyses the peroxyflavin-independent oxygenation-dehydrogenation dual oxidation of a highly reactive poly(β-carbonyl). The crystal structure of EncM with bound substrate mimics and isotope labelling studies reveal previously unknown flavin redox biochemistry. We show that EncM maintains an unexpected stable flavin-oxygenating species, proposed to be a flavin-N5-oxide, to promote substrate oxidation and trigger a rare Favorskii-type rearrangement that is central to the biosynthesis of the antibiotic enterocin. This work provides new insight into the fine-tuning of the flavin cofactor in offsetting the innate reactivity of a polyketide substrate to direct its efficient electrocyclization.

PubMed: 24162851
DOI: 10.1038/nature12643

実験手法

X-RAY DIFFRACTION (1.82 Å)