Enantiocomplementary C–H Bond Hydroxylation Combining Photo‐Catalysis and Whole‐Cell Biocatalysis in a One‐Pot Cascade Process

Enantiocomplementary hydroxylation of alkyl aromatics through a one‐pot photo‐biocatalytic cascade reaction is described. The photoredox process is implemented in aqueous phase with O 2 as oxidant and the subsequent ( R )‐ or ( S )‐selective bioreduction is performed by whole cell system without the addition of the expensive cofactor (NADPH). This mild, operationally simple protocol transforms a wide variety of readily available aromatic compounds into valuable chiral alcohols with high yield (up to 90 %) and stereoselectivity (up to 99 %), thereby displaying important potentials in organic synthesis.