Photoredox and Nickel Dual Catalysis in Organic Synthesis

Photoredox and nickel dual catalysis merges visible-light-driven photocatalysis with nickel-mediated cross-coupling to enable bond constructions that are difficult under conventional conditions. In this approach, a photocatalyst absorbs light to undergo single-electron transfer (SET), generating radical species from stable precursors. These radicals are then intercepted by a nickel complex, which undergoes oxidative addition, radical capture and reductive elimination to forge new C–C or C–X bonds. The separation of radical generation and bond formation permits milder reaction conditions, broad functional-group tolerance and enhanced selectivity. Applications span sp2–sp3 cross-couplings, C–H functionalisation, cascade processes and decarboxylative alkylations. Advances in catalyst design, mechanistic understanding and reactor engineering—particularly continuous-flow photoreactors—have improved efficiency and scalability, positioning dual catalysis as a sustainable platform for complex molecule synthesis in both academic and industrial settings.

Research from Nature Portfolio

A new protocol for light-mediated Suzuki–Miyaura cross-coupling demonstrates the power of photoredox and nickel dual catalysis to assemble C(sp2)–C(sp3) bonds under exceptionally mild and rapid conditions. Simple alkenes are converted to alkyl boranes by hydroboration and then coupled with aryl bromides at room temperature in under 30 minutes, without reliance on expensive or air-sensitive reagents. The method displays excellent regioselectivity and broad substrate scope, and its translation to continuous-flow operation enhances safety, throughput and reproducibility. This scalable approach to sp3-rich scaffolds holds particular promise for accelerating medicinal chemistry campaigns.

Photoredox and Nickel Dual Catalysis in Organic Synthesis publication trend

The graph below shows the total number of articles in photoredox and nickel dual catalysis in organic synthesis across all publications each year (not limited to Nature Index journals).

Technical terms

Photoredox catalysis: Use of light-absorbing catalysts to drive single-electron transfer steps that generate reactive radical intermediates.

Nickel catalysis: Employment of nickel complexes to mediate bond formation via oxidative addition, radical capture and reductive elimination.

Single-electron transfer (SET): Mechanism in which one electron is transferred between species, initiating radical pathways.

Cross-coupling: Metal-catalysed reaction joining two molecular fragments, often forming a new carbon–carbon bond.

Cascade reaction: Series of sequential transformations conducted in one vessel without isolating intermediates.

Continuous flow: Reaction engineering strategy in which reagents flow through a reactor, improving heat and photon management for photochemical processes.

References

1. Rapid and scalable photocatalytic C(sp2)–C(sp3) Suzuki−Miyaura cross-coupling of aryl bromides with alkyl boranes. Nature Communications (2024).
2. Cascade Cross‐Coupling of Dienes: Photoredox and Nickel Dual Catalysis. Angewandte Chemie International Edition (2019).
3. C–H functionalization of amines with aryl halides by nickel-photoredox catalysis. Chemical Science (2016).
4. Ligand functionalization as a deactivation pathway in a fac -Ir(ppy) 3 -mediated radical addition. Chemical Science (2015).
5. Rapid Optimization of Photoredox Reactions for Continuous-Flow Systems Using Microscale Batch Technology. ACS Central Science (2021).