Pienaar, Daniel P.Mitra, Robin K.Botes, Adriana L.Brady, Dean2024-11-182024-11-182025Daniel P. Pienaar, Robin K. Mitra, Adriana L. Botes & Dean Brady (2025) A highly efficient chemoenzymatic process to produce (R)-6,7-dihydroxygeraniol, Biocatalysis and Biotransformation, 43:1, 109-116, DOI: 10.1080/10242422.2024.2410780.1024-2422 (print)1029-2446 (online)10.1080/10242422.2024.2410780http://hdl.handle.net/2263/99112The efficient asymmetric dihydroxylation of 6,7-epoxygeraniol was performed using a chemoenzymatic process employing a yeast epoxide hydrolase (EH) resolution stereoinversion step, followed by stereoretentive chemical hydrolysis of the remaining epoxide to produce (6 R)-6,7-dihydroxygeraniol at unprecedented high enantiometic excess (ee) (>97.5%) and high isolated yield (72 mol % overall yield over 5 steps from commercially available geraniol). The enzymatic process was completed within 2 h at 250 g/L substrate loading reaching > 49.5 mass % conversion of the racemic epoxide. The reaction was self-limiting and furnished both the homochiral (6 R)-triol and the residual (6 R)-epoxide at > 99% ee, due to enantio-inversion of the (6S)-epoxide. The (6 R)-epoxide was subsequently chemically hydrolysed, without first needing to separate the epoxide and triol products, to afford the desired (6 R)-triol product in >97.5% ee, at multigram scale. This chemoenzymatic procedure offers an excellent alternative to chemical asymmetric epoxidation or dihydroxylation for the production of enantiopure 6,7-dihydroxygeranyl and 6,7-epoxygeranyl type compounds in general. It exemplifies the benefits of using greener EH bioprocesses to produce such compounds in high ee’s and high isolated yields.en© 2024 The Author(s). This is an Open Access article distributed under the terms of the Creative Commons Attribution-NonCommercial-NoDerivatives License.Asymmetric biocatalysisChemoenzymatic synthesisDihydroxygeranylEpoxideArticle