Description:
<jats:title>Abstract</jats:title><jats:p>We report on a ‘green’ method for the utilization of carbon dioxide as C<jats:sub>1</jats:sub> unit for the regioselective synthesis of (<jats:italic>E</jats:italic>)‐cinnamic acids <jats:italic>via</jats:italic> regioselective enzymatic carboxylation of <jats:italic>para</jats:italic>‐hydroxystyrenes. Phenolic acid decarboxylases from bacterial sources catalyzed the β‐carboxylation of <jats:italic>para</jats:italic>‐hydroxystyrene derivatives with excellent regio‐ and (<jats:italic>E</jats:italic>/<jats:italic>Z</jats:italic>)‐stereoselectivity by exclusively acting at the β‐carbon atom of the C=C side chain to furnish the corresponding (<jats:italic>E</jats:italic>)‐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.</jats:p><jats:p><jats:boxed-text content-type="graphic" position="anchor"><jats:graphic xmlns:xlink="http://www.w3.org/1999/xlink" mimetype="image/png" position="anchor" specific-use="enlarged-web-image" xlink:href="graphic/adsc201401028-toc-0001-m.png"><jats:alt-text>magnified image</jats:alt-text></jats:graphic></jats:boxed-text>
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