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Efficient photoredox catalysis in C-C cross-coupling reactions by two-coordinated Au(I) complex
Byung Hak Jhun1, Jihoon Jang2, Shinae Lee1
1Department of Chemical and Biomolecular Engineering, Yonsei University, Seoul, 03722, Republic of Korea.
Nature Communications
|August 3, 2024
Summary
New gold(I) catalysts enable efficient C-C cross-coupling reactions using visible light. These photocatalysts, featuring ligand-to-ligand charge-transfer, offer strong redox power and long excited-state lifetimes for diverse organic synthesis applications.
Area of Science:
- Organic Chemistry
- Photocatalysis
- Organometallic Chemistry
Background:
- Photocatalysis is crucial for redox activation in organic synthesis.
- Developing catalysts with enhanced oxidizing/reducing power and long excited-state lifetimes is essential for expanding photoredox catalysis.
- Strongly cathodic oxidation potentials and prolonged excited-state lifetimes are highly sought after in photocatalyst design.
Purpose of the Study:
- To introduce and investigate two-coordinate gold(I) complex photocatalysts for C-C cross-coupling reactions.
- To demonstrate the catalytic utility of catalysts featuring ligand-to-ligand charge-transfer (LLCT) transitions.
- To broaden the scope of photoredox catalysis using novel gold complexes.
Main Methods:
- Utilized two-coordinate gold(I) complexes as photocatalysts.
- Investigated C-C cross-coupling reactions between N-heterocycles and (hetero)aryl halides under visible-light irradiation.
- Conducted mechanistic studies including direct spectroscopic evidence for catalytic steps.
Main Results:
- Demonstrated efficient C-C cross-coupling of N-heterocycles and (hetero)aryl halides, including challenging substrates like aryl chlorides.
- Achieved high yields (91%) with low catalyst loading (0.1 mol%) under visible light.
- Characterized catalysts with strong visible-light absorption and a long excited-state lifetime (210 ns).
Conclusions:
- Two-coordinate Au(I) complex photocatalysts with LLCT transitions are effective for C-C cross-coupling.
- These catalysts offer significant advantages, including broad substrate scope, high selectivity, and robust excited-state properties.
- The findings provide insights for future applications of LLCT-active Au(I) complexes in organic synthesis.
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