Asymmetric Electrochemical Catalysis

The quest for enantioenriched molecules has spurred innovation at the interface between electrochemistry and asymmetric catalysis. Asymmetric electrochemical catalysis harnesses controlled electron flow to activate substrates, leveraging chiral catalysts to steer reaction pathways towards one enantiomer. This approach replaces stoichiometric chemical reagents with electrons as traceless redox agents, enhancing atom economy and sustainability. Through precise tuning of electrode potentials and catalyst environments, a range of enantioselective transformations—from C–C and C–X bond formations to cyclisations—have been realised. Recent advances integrate photoredox and phase-transfer strategies, enabling weak interactions to dictate stereocontrol in electrochemical media. Collectively, these developments underscore the global significance of this platform for constructing chiral building blocks in pharmaceuticals and natural product synthesis, offering greener and more economical alternatives to conventional asymmetric methods.

Research from Nature Portfolio

Recent studies have demonstrated nickel–biimidazole complexes mediating electroreductive cross-coupling of aryl aziridines with aryl iodides under undivided cell conditions, delivering β-phenethylamines with high enantioselectivity and broad functional-group tolerance via an electroreduction-mediated catalyst turnover. Another approach employed a chiral phosphate phase-transfer catalyst to achieve weak-interaction-driven asymmetric bromocyclisation, synchronising anodic oxidation, ion-pair formation and bromination to furnish cyclic bromides with excellent enantiomeric excess. Additionally, a synergistic photoredox–cobalt–amine system has enabled direct asymmetric dehydrogenative C(sp3)–H alkenylation of carbonyl substrates under visible light, exploiting a chiral α-imino radical to achieve high yields and stereoselectivities in one annulation step.

Asymmetric Electrochemical Catalysis publication trend

The graph below shows the total number of articles in asymmetric electrochemical catalysis across all publications each year (not limited to Nature Index journals).

Technical terms

Electrosynthesis: Synthesis of organic molecules using electrochemical methods to provide redox equivalents via electrodes.

Enantioselectivity: Preferential formation of one enantiomer over its mirror image in a chiral reaction.

Electrode potential: Voltage applied to an electrode determining the direction and rate of redox processes.

Chiral catalyst: Catalyst possessing asymmetry that induces stereocontrol in a reaction.

Phase-transfer catalysis: Technique that facilitates reaction between species in different phases through a transfer agent.

References

1. Nickel/biimidazole-catalyzed electrochemical enantioselective reductive cross-coupling of aryl aziridines with aryl iodides. Nature Communications (2023).
2. Electricity-driven asymmetric bromocyclization enabled by chiral phosphate anion phase-transfer catalysis. Nature Communications (2023).
3. Asymmetric C–H Dehydrogenative Alkenylation via a Photo-induced Chiral α‑Imino Radical Intermediate. Nature Communications (2024).
4. Electrochemically Driven Nickel‐Catalyzed Enantioselective Hydro‐Arylation/Alkenylation of Enones. Advanced Science (2024).
5. A review of asymmetric synthetic organic electrochemistry and electrocatalysis: concepts, applications, recent developments and future directions. Beilstein Journal of Organic Chemistry (2019).