Photoenzymatic Catalysis in Asymmetric Organic Synthesis

Photoenzymatic catalysis harnesses the synergy between light‐driven activation and enzyme‐mediated transformation to achieve highly selective asymmetric syntheses under mild, sustainable conditions. In these systems, a photocatalyst or photoactive cofactor absorbs visible light to generate reactive intermediates, such as radicals or excited‐state electron donors, which are then channelled by an enzyme’s chiral active site. This approach not only broadens the palette of biocatalytic reactions—encompassing C–H functionalisation, radical cyclisation and carbon–carbon bond cleavage—but also permits in situ regeneration of cofactors, minimising waste and energy input. Photoenzymatic cascades can be executed in one pot, integrating photochemical steps with enzymatic turnovers to furnish enantiopure products with high atom economy. The technique holds particular promise for the synthesis of chiral alcohols, amines and heterocycles of pharmaceutical relevance, offering a renewable alternative to conventional metal‐based asymmetric catalysts and aligning with global goals for greener chemical manufacturing.

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Photoenzymatic Catalysis in Asymmetric Organic Synthesis publication trend

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Technical terms

Photoactivation: Initiation of a chemical reaction by absorption of light leading to excited‐state species.

Photoredox catalysis: Light‐driven electron‐transfer processes that generate radical intermediates.

Enantioselectivity: Preferential formation of one enantiomer over the other in a chiral reaction.

Cofactor regeneration: In situ recycling of enzyme cofactors (e.g. NAD(P)H) to sustain multiple catalytic turnovers without external reagents.

Radical cyclisation: Intramolecular bond‐forming step involving radical intermediates to produce ring systems.

References

1. Photo‐biocatalytic Cascades: Combining Chemical and Enzymatic Transformations Fueled by Light. ChemBioChem (2020).
2. A De Novo Metalloenzyme for Cerium Photoredox Catalysis. Journal of the American Chemical Society (2024).
3. Photocatalytic Oxidative Cleavage of Alkenes Followed by Carbonyl Stereoselective Bioreduction for the Synthesis of Enantioenriched Secondary Alcohols. Advanced Synthesis & Catalysis (2024).
4. Evidence of a Distinctive Enantioselective Binding Mode for the Photoinduced Radical Cyclization of α‑Chloroamides in Ene-Reductases. ACS Catalysis (2023).