Tunable Production of ( R )- or ( S )-Citronellal from Geraniol via a Bienzymatic Cascade Using a Copper Radical Alcohol Oxidase and Old Yellow Enzyme

David Ribeaucourt (1) , Georg Höfler (2) , Mehdi Yemloul (3) , Bastien Bissaro (1) , Fanny Lambert (4) , Jean-Guy Berrin (1) , Mickael Lafond (3) , Caroline Paul (2)

1 BBF - Biodiversité et Biotechnologie Fongiques
2 Catalysis Engineering - ChemE, Delft University of Technology, Van der Maasweg 9, 2629HZ Delft
3 ISM2 - Institut des Sciences Moléculaires de Marseille
4 V MANE Fils

Biocatalytic pathways for the synthesis of (-)-menthol, the most sold flavor worldwide, are highly sought-after. To access the key intermediate (R)-citronellal used in current major industrial production routes, we established a one-pot bienzymatic cascade from inexpensive geraniol, overcoming the problematic biocatalytic reduction of the mixture of (E/Z)-isomers in citral by harnessing a copper radical oxidase (CgrAlcOx) and an old yellow enzyme (OYE). The cascade using OYE2 delivered 95.1% conversion to (R)-citronellal with 95.9% cc, a 62 mg scaleup affording high yield and similar optical purity. An alternative OYE, GIuER, gave (S)-citronellal from geraniol with 95.3% conversion and 99.2% ee.

Mots clés: biocatalysis biocascade citronellal citral geranial enzymatic oxidation enzymatic reduction

Domaines: Biotechnologies

David Ribeaucourt, Georg Höfler, Mehdi Yemloul, Bastien Bissaro, Fanny Lambert, et al.. Tunable Production of ( R )- or ( S )-Citronellal from Geraniol via a Bienzymatic Cascade Using a Copper Radical Alcohol Oxidase and Old Yellow Enzyme. ACS Catalysis, 2022, 12 (2), pp.1111-1116. ⟨10.1021/acscatal.1c05334⟩. ⟨hal-03582992⟩