title: Regioselective Enzymatic β-Carboxylation ofpara-Hydroxy- styrene Derivatives Catalyzed by Phenolic Acid Decarboxylases.
abstract: We report on a 'green' method for the utilization of carbon dioxide as C1unit for the regioselective synthesis of (E)-cinnamic acidsviaregioselective enzymatic carboxylation ofpara-hydroxystyrenes. Phenolic acid decarboxylases from bacterial sources catalyzed the β-carboxylation ofpara-hydroxystyrene derivatives with excellent regio- and (E/Z)-stereoselectivity by exclusively acting at the β-carbon atom of the C=C side chain to furnish the corresponding (E)-cinnamic acid derivatives in up to 40% conversion at the expense of bicarbonate as carbon dioxide source. Studies on the substrate scope of this strategy are presented and a catalytic mechanism is proposed based on molecular modelling studies supported by mutagenesis of amino acid residues in the active site.
authors.affiliation: Austrian Centre of Industrial Biotechnology, c/o Department of Chemistry, Organic & Bioorganic Chemistry, Heinrichstrasse 28, University of Graz 8010 Graz, Austria ; Department of Chemistry, Organic & Bioorganic Chemistry, Heinrichstrasse 28, University of Graz 8010 Graz, Austria, ; phone: (+43)-316-380-5332 ; e-mail: Si.Glueck@Uni-Graz.at or Kurt.Faber@Uni-Graz.at.
authors.forename: Christiane
authors.initials: C
authors.lastname: Wuensch
authors.affiliation: Austrian Centre of Industrial Biotechnology, c/o Department of Chemistry, Organic & Bioorganic Chemistry, Heinrichstrasse 28, University of Graz 8010 Graz, Austria ; Institute of Molecular Biosciences, Humboldtstrasse 50, University of Graz 8010 Graz, Austria.
authors.forename: Tea
authors.initials: T
authors.lastname: Pavkov-Keller
authors.affiliation: Austrian Centre of Industrial Biotechnology, c/o Department of Chemistry, Organic & Bioorganic Chemistry, Heinrichstrasse 28, University of Graz 8010 Graz, Austria ; Institute of Molecular Biosciences, Humboldtstrasse 50, University of Graz 8010 Graz, Austria.
authors.forename: Georg
authors.initials: G
authors.lastname: Steinkellner
authors.affiliation: Austrian Centre of Industrial Biotechnology, c/o Department of Chemistry, Organic & Bioorganic Chemistry, Heinrichstrasse 28, University of Graz 8010 Graz, Austria ; Department of Chemistry, Organic & Bioorganic Chemistry, Heinrichstrasse 28, University of Graz 8010 Graz, Austria, ; phone: (+43)-316-380-5332 ; e-mail: Si.Glueck@Uni-Graz.at or Kurt.Faber@Uni-Graz.at.
authors.forename: Johannes
authors.initials: J
authors.lastname: Gross
authors.affiliation: Department of Chemistry, Organic & Bioorganic Chemistry, Heinrichstrasse 28, University of Graz 8010 Graz, Austria, ; phone: (+43)-316-380-5332 ; e-mail: Si.Glueck@Uni-Graz.at or Kurt.Faber@Uni-Graz.at.
authors.forename: Michael
authors.initials: M
authors.lastname: Fuchs
authors.affiliation: Austrian Centre of Industrial Biotechnology, c/o Department of Chemistry, Organic & Bioorganic Chemistry, Heinrichstrasse 28, University of Graz 8010 Graz, Austria ; Institute of Molecular Biosciences, Humboldtstrasse 50, University of Graz 8010 Graz, Austria.
authors.forename: Altijana
authors.initials: A
authors.lastname: Hromic
authors.affiliation: Austrian Centre of Industrial Biotechnology, c/o Department of Chemistry, Organic & Bioorganic Chemistry, Heinrichstrasse 28, University of Graz 8010 Graz, Austria ; Institute of Molecular Biosciences, Humboldtstrasse 50, University of Graz 8010 Graz, Austria.
authors.forename: Andrzej
authors.initials: A
authors.lastname: Lyskowski
authors.affiliation: Austrian Centre of Industrial Biotechnology, c/o Department of Chemistry, Organic & Bioorganic Chemistry, Heinrichstrasse 28, University of Graz 8010 Graz, Austria ; Institute of Molecular Biosciences, Humboldtstrasse 50, University of Graz 8010 Graz, Austria.
authors.forename: Kerstin
authors.initials: K
authors.lastname: Fauland
authors.affiliation: Institute of Molecular Biosciences, Humboldtstrasse 50, University of Graz 8010 Graz, Austria.
authors.forename: Karl
authors.initials: K
authors.lastname: Gruber
authors.affiliation: Austrian Centre of Industrial Biotechnology, c/o Department of Chemistry, Organic & Bioorganic Chemistry, Heinrichstrasse 28, University of Graz 8010 Graz, Austria ; Department of Chemistry, Organic & Bioorganic Chemistry, Heinrichstrasse 28, University of Graz 8010 Graz, Austria, ; phone: (+43)-316-380-5332 ; e-mail: Si.Glueck@Uni-Graz.at or Kurt.Faber@Uni-Graz.at.
authors.forename: Silvia M
authors.initials: SM
authors.lastname: Glueck
authors.affiliation: Department of Chemistry, Organic & Bioorganic Chemistry, Heinrichstrasse 28, University of Graz 8010 Graz, Austria, ; phone: (+43)-316-380-5332 ; e-mail: Si.Glueck@Uni-Graz.at or Kurt.Faber@Uni-Graz.at.
authors.forename: Kurt
authors.initials: K
authors.lastname: Faber
keywords: biotransformations; enzyme catalysis; para-hydroxystyrenes; phenolic acid decarboxylases; reaction mechanism; regioselective carboxylation