PPM-Level Palladium-Catalyzed Sonogashira Coupling Promoted by Fe3(CO)12 and α,β-Ynone Ligands
- 1Faculty of Medical Laboratory Science, Shanxi College of Medicine, Fenyang 032200, China
- 2Key Laboratory of Applied Surface and Colloid Chemistry (MOE), Xi’an Key Laboratory of Organometallic Material Chemistry, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710119, China
- 3School of Chemistry & Environment, Ankang University, Ankang 725000, China
Abstract
The development of sustainable cross-coupling methodologies that drastically reduce reliance on precious metals represents a central challenge in modern synthetic chemistry. Here we report a synergistic Pd/Fe bimetallic catalytic system for Sonogashira coupling that operates at a palladium loading of 200 ppm PdCl2 in conjunction with 0.1 mol% Fe3(CO)12. Using α,β-ynone ligands in methanol at 60 °C, this system achieves 69% to 98% yield across 24 examples encompassing diverse aryl iodides and terminal alkynes. Catalytic experiments reveal that Fe3(CO)12 is uniquely effective among iron sources, with its cluster structure proving essential for the observed rate enhancement, while the α,β-ynone ligands improve catalytic performance relative to ligand-free conditions. Ligand structure–activity studies identify L6 (3-(4-bromophenyl)-1-(4-methoxyphenyl)prop-yn-1-one), bearing a 4-methoxybenzoyl and 4-bromophenylethenyl motif, as the optimal ligand, affording 98% yield. The system exhibits broad functional group tolerance, accommodating both electron-rich and electron-deficient aryl iodides, while higher yields are achieved when using aryl-acetylenes as compared with their alkyl- analogs. This work demonstrates that the combination of an iron carbonyl cluster additive with tailored α,β-ynone ligands enables a dramatic reduction in noble metal loading while maintaining high catalytic efficiency under mild conditions, offering a practical and sustainable route to aryl alkynes.
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BibTeX
@article{yu2026ppmlevel,
title = {{PPM-Level Palladium-Catalyzed Sonogashira Coupling Promoted by Fe3(CO)12 and α,β-Ynone Ligands}},
author = {Bo Yu and Xian Wang and Hongyu Yang and Kan Zhang and Weiqiang Zhang},
journal = {Catalysts},
year = {2026},
month = oct,
doi = {10.3390/catal16100895},
url = {https://www.mdpi.com/2073-4344/16/10/895},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - PPM-Level Palladium-Catalyzed Sonogashira Coupling Promoted by Fe3(CO)12 and α,β-Ynone Ligands
AU - Bo Yu
AU - Xian Wang
AU - Hongyu Yang
AU - Kan Zhang
AU - Weiqiang Zhang
PY - 2026
DA - 2026/10/09
JO - Catalysts
DO - 10.3390/catal16100895
UR - https://www.mdpi.com/2073-4344/16/10/895
AB - The development of sustainable cross-coupling methodologies that drastically reduce reliance on precious metals represents a central challenge in modern synthetic chemistry. Here we report a synergistic Pd/Fe bimetallic catalytic system for Sonogashira coupling that operates at a palladium loading of 200 ppm PdCl2 in conjunction with 0.1 mol% Fe3(CO)12. Using α,β-ynone ligands in methanol at 60 °C, this system achieves 69% to 98% yield across 24 examples encompassing diverse aryl iodides and terminal alkynes. Catalytic experiments reveal that Fe3(CO)12 is uniquely effective among iron sources, with its cluster structure proving essential for the observed rate enhancement, while the α,β-ynone ligands improve catalytic performance relative to ligand-free conditions. Ligand structure–activity studies identify L6 (3-(4-bromophenyl)-1-(4-methoxyphenyl)prop-yn-1-one), bearing a 4-methoxybenzoyl and 4-bromophenylethenyl motif, as the optimal ligand, affording 98% yield. The system exhibits broad functional group tolerance, accommodating both electron-rich and electron-deficient aryl iodides, while higher yields are achieved when using aryl-acetylenes as compared with their alkyl- analogs. This work demonstrates that the combination of an iron carbonyl cluster additive with tailored α,β-ynone ligands enables a dramatic reduction in noble metal loading while maintaining high catalytic efficiency under mild conditions, offering a practical and sustainable route to aryl alkynes.
SN - 2073-4344
ER -