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High-Density Palladium Single-Atom Catalysts for Photoinduced Tandem Decarbonylation/Carbonylative Reductive Coupling
Haolin Du1,2,3, Qi Yu4, Yucong Miao2,5
1Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, Fuzhou 350207, P. R. China.
Journal of the American Chemical Society
|December 12, 2025
Summary
This study introduces a new carbonylative reductive coupling reaction using pivaldehyde and water as reactants. A novel palladium-functionalized carbon nitride catalyst enables efficient cascade reactions and sustainable synthesis of pharmaceuticals.
Area of Science:
- Catalysis
- Organic Chemistry
- Materials Science
Background:
- Carbonylation reactions typically require carbon monoxide (CO) or CO surrogates.
- Developing sustainable and cost-effective carbonyl sources and reductants is crucial for green chemistry.
Purpose of the Study:
- To report a novel carbonylative reductive coupling reaction using pivaldehyde and water.
- To develop a multifunctional catalytic system for cascade organic transformations.
- To demonstrate the synthesis of pharmaceutical compounds using this new method.
Main Methods:
- Utilizing pivaldehyde as a carbonyl source and water as a reductant.
- Designing a polymeric carbon nitride semiconductor functionalized with high-density single-atom palladium as a photocatalyst.
- Employing computational studies to understand reaction mechanisms and catalyst performance.
- Conducting life cycle assessment for economic viability.
Main Results:
- A novel cascade decarbonylation-CO migration-carbonylative coupling process was achieved.
- Photocatalytic water oxidation supplied electrons for the reductive coupling.
- The catalyst demonstrated high stability over 10 cycles.
- Efficient synthesis of pharmaceutical compounds, including AdipoRon, was demonstrated on a decagram scale.
Conclusions:
- The developed method offers an economically viable and sustainable approach to carbonylative reductive coupling.
- Single-atom photocatalysts show significant potential for advancing sustainable cascade organic transformations.
- The catalyst's high-density single-atom palladium configuration is key to efficient CO migration.
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