Biocatalytic Aromaticity-Breaking Epoxidation of Naphthalene and Nucleophilic Ring-Opening Reactions

Biocatalytic Aromaticity-Breaking Epoxidation of Naphthalene and Nucleophilic Ring-Opening Reactions

Zhang, W. (TU Delft BT/Biocatalysis; Chinese Academy of Sciences)
Li, Huanhuan (Xi’an Jiaotong University)
Younes, S.H.H. (TU Delft BT/Biocatalysis; Sohag University)
Gómez De Santos, Patricia (Institute of Catalysis, CSIC, Madrid)
Tieves, F. (TU Delft BT/Biocatalysis)
Grogan, Gideon (University of York)
Pabst, Martin (TU Delft BT/Environmental Biotechnology)
Alcalde, Miguel (Institute of Catalysis, CSIC, Madrid)
Whitwood, Adrian C. (University of York)
Hollmann, F. (TU Delft BT/Biocatalysis)

2021

Aromatic hydroxylation reactions catalyzed by heme-thiolate enzymes proceed via an epoxide intermediate. These aromatic epoxides could be valuable building blocks for organic synthesis giving access to a range of chiral trans-disubstituted cyclohexadiene synthons. Here, we show that naphthalene epoxides generated by fungal peroxygenases can be subjected to nucleophilic ring opening, yielding non-racemic trans-disubstituted cyclohexadiene derivates, which in turn can be used for further chemical transformations. This approach may represent a promising shortcut for the synthesis of natural products and APIs.

arene epoxides
arene oxyfunctionalization
biocatalysis
chemoenzymatic reactions
naphthalene epoxides
oxidation
peroxygenase

http://resolver.tudelft.nl/uuid:9f3d3442-e0b9-4e90-9d9a-12a7146104cd

https://doi.org/10.1021/acscatal.0c05588

2155-5435

ACS Catalysis, 11 (5), 2644-2649

Institutional Repository

journal article

© 2021 W. Zhang, Huanhuan Li, S.H.H. Younes, Patricia Gómez De Santos, F. Tieves, Gideon Grogan, Martin Pabst, Miguel Alcalde, Adrian C. Whitwood, F. Hollmann