Rieske non-heme iron dioxygenases are fascinating enzymes, which are able to oxyfunctionalize aromatic compounds via a dearomatizing cis-dihydroxylation reaction. The generated valuable cis-diols find numerous applications in synthetic organic chemistry, primary as synthons for pharmaceuticals. By semi-rational evolution, we lighted up the toluene dioxygenase (TDO) capability to convert bulkier compounds at unprecedented reported conversions. Here, we provide a set of novel TDO-based biocatalysts useful for the preparation of oxyfunctionalized bicyclic scaffolds, which are valuable to perform downstream synthetic processes.
Advanced Synthesis and Catalysis https://doi.org/10.1002/adsc.