Photobiocatalytic Platform\nfor the Efficient Enantio-Divergent\nSynthesis of β‑Fluoromethylated Ketones

β-Fluoromethyl (CH<sub>2</sub>F, CHF<sub>2</sub>, and CF<sub>3</sub>)-substituted chiral ketones are essential moieties\nand are\nvital building blocks in pharmaceutical and agrochemistry. However,\ngeneral and convenient methods for enantio-diverse access to diverse\nβ-fluoromethylated ketones are lacking, hindering the further\ndevelopment of these functional moieties. In this study, we developed\nan ene-reductase-based photobiocatalytic platform for efficient synthesis\nof enantio-divergent β-fluoromethylated chiral ketones. Our\nmethod highlights substrate-type diversity, excellent enantioselectivity,\nenzymatic enantio-divergent synthesis, as well as a dicyanopyrazine\n(DPZ)-type photosensitizer for biocompatible olefin <i>E</i>/<i>Z</i> isomerization in enzymatic stereoconvergent olefin\nasymmetric reduction, thereby providing a general photobiocatalytic\nsolution to diverse β-fluoromethylated chiral ketones.