Journal Article

PUBDB-2017-10734

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Regioselective para-Carboxylation of Catechols by a Prenylated Flavin Dependent Decarboxylase

Payer, S. ; Marshall, S. A. ; Bärland, N. ; Sheng, X. ; Reiter, T. ; Dordic, A.Extern* ; Steinkellner, G. ; Wuensch, C. ; Kaltwasser, S. ; Fisher, K. ; Rigby, S. E. J. ; Macheroux, P. ; Vonck, J. ; Gruber, K. ; Faber, K. ; Himo, F. ; Leys, D. ; Pavkov-Keller, T. (Corresponding author)Extern* ; Glueck, S. M. (Corresponding author)

2017
Wiley-VCH Weinheim

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Please use a persistent id in citations: doi:10.1002/anie.201708091  doi:10.3204/PUBDB-2017-10734

Abstract: The utilization of CO$-2$ as a carbon source for organic synthesis meets the urgent demand for more sustainability in the production of chemicals. Herein, we report on the enzyme-catalyzed para-carboxylation of catechols, employing 3,4-dihydroxybenzoic acid decarboxylases (AroY) that belong to the UbiD enzyme family. Crystal structures and accompanying solution data confirmed that AroY utilizes the recently discovered prenylated FMN (prFMN) cofactor, and requires oxidative maturation to form the catalytically competent prFMN4$^{iminium}$ species. This study reports on the in vitro reconstitution and activation of a prFMN-dependent enzyme that is capable of directly carboxylating aromatic catechol substrates under ambient conditions. A reaction mechanism for the reversible decarboxylation involving an intermediate with a single covalent bond between a quinoid adduct and cofactor is proposed, which is distinct from the mechanism of prFMN-associated 1,3-dipolar cycloadditions in related enzymes.

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Contributing Institute(s):

1. DOOR-User (DOOR)

Research Program(s):

1. 6G3 - PETRA III (POF3-622) (POF3-622)

Experiment(s):

1. PETRA Beamline P11 (PETRA III)

Appears in the scientific report 2017

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Database coverage:
; ; ; Current Contents - Life Sciences ; Current Contents - Physical, Chemical and Earth Sciences ; IF >= 10 ; JCR ; NCBI Molecular Biology Database ; Nationallizenz ; SCOPUS ; Science Citation Index ; Science Citation Index Expanded ; Thomson Reuters Master Journal List ; Web of Science Core Collection

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