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The synthesis approach starts from a readily accessible cinnamic acid ester that is converted using a rhodium\u2010based hydroformylation catalyst toward the corresponding chiral aldehyde. This compound is subsequently converted via a transaminase\u2010catalyzed reaction system that yields the desired \u03b2\u2010chiral amino acid ester and the final free \u03b2\u2010chiral amino acid (<jats:italic><jats:sc>S<\/jats:sc><\/jats:italic><jats:sc>)\u2010<\/jats:sc>baclofen after a simple hydrolysis reaction. This synthesis concept does provide high atom efficiency and does not require an additional chiral resolution step of a racemic product.<\/jats:p>","DOI":"10.1002\/cbic.202500108","type":"journal-article","created":{"date-parts":[[2025,6,12]],"date-time":"2025-06-12T13:38:34Z","timestamp":1749735514000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Chemoenzymatic Route toward a De\u2009Novo Enantioselective Total Synthesis of (<i>S<\/i>)\u2010Baclofen Based on Metal\u2010Catalyzed Hydroformylation and Enzymatic Transamination"],"prefix":"10.1002","volume":"26","author":[{"given":"Feodor","family":"Belov","sequence":"first","affiliation":[{"name":"Institute of Chemistry Biocatalytic Synthesis Group Otto von Guericke University of Magdeburg  Building 28, Universit\u00e4tsplatz 2 39106 Magdeburg Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Hannah","family":"Bork","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry Bielefeld University  Universit\u00e4tsstrasse 25 33615 Bielefeld Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Luise","family":"H\u00e4nel","sequence":"additional","affiliation":[{"name":"Institute of Biochemistry Protein Biochemistry Group University of Greifswald  Felix\u2010Hausdorff\u2010Str. 4 17489 Greifswald Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Manideep V.","family":"Kollipara","sequence":"additional","affiliation":[{"name":"Institute of Biochemistry Protein Biochemistry Group University of Greifswald  Felix\u2010Hausdorff\u2010Str. 4 17489 Greifswald Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2542-725X","authenticated-orcid":false,"given":"Matthias","family":"H\u00f6hne","sequence":"additional","affiliation":[{"name":"Institute of Chemistry Biocatalysis Group Technical University of Berlin  M\u00fcller\u2010Breslau\u2010Strasse 10 10623 Berlin Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8582-2107","authenticated-orcid":false,"given":"Harald","family":"Gr\u00f6ger","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry Bielefeld University  Universit\u00e4tsstrasse 25 33615 Bielefeld Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9302-9803","authenticated-orcid":false,"given":"Jan","family":"von Langermann","sequence":"additional","affiliation":[{"name":"Institute of Chemistry Biocatalytic Synthesis Group Otto von Guericke University of Magdeburg  Building 28, Universit\u00e4tsplatz 2 39106 Magdeburg Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2025,7,4]]},"reference":[{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1055\/b-003-108611"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1080\/17518250903258150"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.cbpa.2010.02.018"},{"key":"e_1_2_7_4_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200300599"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1002\/9783527807253"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.3389\/fctls.2023.1359527"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1002\/3527608184"},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1002\/9783527639861"},{"key":"e_1_2_7_8_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201612462"},{"key":"e_1_2_7_8_3","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201702235"},{"journal-title":"Green Synth. 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