Regioselective para-Carboxylation of Catechols with a Prenylated Flavin Dependent Decarboxylase

被引：63

作者：

Payer, Stefan E. ^{[1
]}

Marshall, Stephen A. ^{[2
]}

Baerland, Natalie ^{[3
]}

Sheng, Xiang ^{[4
]}

Reiter, Tamara ^{[7
]}

Dordic, Andela ^{[5
,7
]}

Steinkellner, Georg ^{[5
,7
]}

Wuensch, Christiane ^{[7
]}

Kaltwasser, Susann ^{[3
]}

Fisher, Karl ^{[2
]}

Rigby, Stephen E. J. ^{[2
]}

Macheroux, Peter ^{[6
]}

Vonck, Janet ^{[3
]}

Gruber, Karl ^{[5
]}

Faber, Kurt ^{[1
]}

Himo, Fahmi ^{[4
]}

Leys, David ^{[2
]}

Pavkov-Keller, Tea ^{[5
,7
]}

Glueck, Silvia M. ^{[1
,7
]}

机构：

[1] Karl Franzens Univ Graz, Dept Chem Organ & Bioorgan Chem, NAWI Graz, BioTechMed Graz, Heinrichstr 28-2, A-8010 Graz, Austria

[2] Univ Manchester, Manchester Inst Biotechnol, 131 Princess St, Manchester M1 7DN, Lancs, England

[3] Max Planck Inst Biophys, Max von Laue Str 3, D-60438 Frankfurt, Germany

[4] Stockholm Univ, Arrhenius Lab, Dept Organ Chem, S-10691 Stockholm, Sweden

[5] Karl Franzens Univ Graz, Inst Mol Biosci, NAWI Graz, BioTechMed Graz, Humboldtstr 50, A-8010 Graz, Austria

[6] Graz Univ Technol, Inst Biochem, Petersgasse 12, A-8010 Graz, Austria

[7] Austrian Ctr Ind Biotechnol, Graz, Austria

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2017年 / 56卷 / 44期

基金：

英国生物技术与生命科学研究理事会; 奥地利科学基金会;

关键词：

biocatalysis; carboxylation; catechols; prenylated FMN; FERULIC ACID DECARBOXYLASE; GAMMA-RESORCYLIC ACID; REVERSIBLE 4-HYDROXYBENZOATE DECARBOXYLASE; CARBON-DIOXIDE; 2,6-DIHYDROXYBENZOATE DECARBOXYLASE; ENZYMATIC CARBOXYLATION; ANAEROBIC DEGRADATION; GENE CLONING; PURIFICATION; MECHANISM;

D O I：

10.1002/anie.201708091

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The utilization of CO2 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(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.

引用

页码：13893 / 13897

页数：5

共 47 条

[1] Biocatalysis for the application of CO2 as a chemical feedstock [J].

Alissandratos, Apostolos ;

Easton, Christopher J. .

BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY, 2015, 11 :2370-2387

[2] Catalysis for the Valorization of Exhaust Carbon: from CO2 to Chemicals, Materials, and Fuels. Technological Use of CO2 [J].

Aresta, Michele ;

Dibenedetto, Angela ;

Angelini, Antonella .

CHEMICAL REVIEWS, 2014, 114 (03) :1709-1742

[3]

Baunach M., 2015, ANGEW CHEM, V127, P12732

[4] Natural 1,3-Dipolar Cycloadditions [J].

Baunach, Martin ;

Hertweck, Christian .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2015, 54 (43) :12550-12552

[5] Unusual reactions involved in anaerobic metabolism of phenolic compounds [J].

Boll, M ;

Fuchs, G .

BIOLOGICAL CHEMISTRY, 2005, 386 (10) :989-997

[6] Evidence for a 1,3-Dipolar Cyclo-addition Mechanism in the Decarboxylation of Phenylacrylic Acids Catalyzed by Ferulic Acid Decarboxylase [J].

Ferguson, Kyle L. ;

Eschweiler, Joseph D. ;

Ruotolo, Brandon T. ;

Marsh, E. Neil G. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2017, 139 (32) :10972-10975

[7] Mechanism of the Novel Prenylated Flavin-Containing Enzyme Ferulic Acid Decarboxylase Probed by Isotope Effects and Linear Free-Energy Relationships [J].

Ferguson, Kyle L. ;

Arunrattanamook, Nattapol ;

Marsh, E. Neil G. .

BIOCHEMISTRY, 2016, 55 (20) :2857-2863

[8] Transition Metal-catalyzed Fixation of Carbon Dioxide via Carbon-carbon Bond Formation [J].

Fujihara, Tetsuaki ;

Tsuji, Yasushi .

JOURNAL OF THE JAPAN PETROLEUM INSTITUTE, 2016, 59 (03) :84-92

[9] Biocatalytic carboxylation [J].

Glueck, Silvia M. ;

Guemues, Selcuc ;

Fabian, Walter M. F. ;

Faber, Kurt .

CHEMICAL SOCIETY REVIEWS, 2010, 39 (01) :313-328

[10] Purification and characterization of an oxygen-sensitive, reversible 3,4-dihydroxybenzoate decarboxylase from Clostridium hydroxybenzoicum [J].

He, ZQ ;

Wiegel, J .

JOURNAL OF BACTERIOLOGY, 1996, 178 (12) :3539-3543

← 1 2 3 4 5 →