Ene‐Reductase: A Multifaceted Biocatalyst in Organic Synthesis

Abstract Biocatalysis integrate microbiologists, enzymologists, and organic chemists to access the repertoire of pharmaceutical and agrochemicals with high chemoselectivity, regioselectivity, and enantioselectivity. The saturation of carbon‐carbon double bonds by biocatalysts challenges the conventional chemical methodology as it bypasses the use of precious metals (in combination with chiral ligands and molecular hydrogen) or organocatalysts. In this line, Ene‐reductases (ERs) from the Old Yellow Enzymes (OYEs) family are found to be a prominent asymmetric biocatalyst that is increasingly used in academia and industries towards unparalleled stereoselective trans ‐hydrogenations of activated C=C bonds. ERs gained prominence as they were used as individual catalysts, multi‐enzyme cascades, and in conjugation with chemical reagents (chemoenzymatic approach). Besides, ERs’ participation in the photoelectrochemical and radical‐mediated process helps to unlock many scopes outside traditional biocatalysis. These up‐and‐coming methodologies entice the enzymologists and chemists to explore, expand and harness the chemistries displayed by ERs for industrial settings. Herein, we reviewed the last five year's exploration of organic transformations using ERs.