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Title | Regioselective para-Carboxylation of Catechols with a Prenylated Flavin Dependent Decarboxylase. |
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Journal, issue, pages | Angew Chem Int Ed Engl, Vol. 56, Issue 44, Page 13893-13897, Year 2017 |
Publish date | Oct 23, 2017 |
Authors | Stefan E Payer / Stephen A Marshall / Natalie Bärland / Xiang Sheng / Tamara Reiter / Andela Dordic / Georg Steinkellner / Christiane Wuensch / Susann Kaltwasser / Karl Fisher / Stephen E J Rigby / Peter Macheroux / Janet Vonck / Karl Gruber / Kurt Faber / Fahmi Himo / David Leys / Tea Pavkov-Keller / Silvia M Glueck / |
PubMed Abstract | The utilization of CO 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- ...The utilization of CO 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 prFMN 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. |
External links | Angew Chem Int Ed Engl / PubMed:28857436 / PubMed Central |
Methods | EM (single particle) / X-ray diffraction |
Resolution | 2.05 - 4.6 Å |
Structure data | EMDB-3718: PDB-5ny5: PDB-5o3m: PDB-5o3n: |
Chemicals | ChemComp-GOL: ChemComp-HOH: ChemComp-9JE: ChemComp-MN: ChemComp-NA: ChemComp-4LU: |
Source |
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Keywords | HYDROLASE / UbiD-family / Carboxylation / Catechols / Prenylated FMN / LYASE / Decarboxylase / prFMN / UbiD |