Reductive Amidation of Nitroarenes on Nitrogen-Coordinated Single-Site Palladium Catalysts
N-aryl amides are essential in pharmaceuticals and fine chemicals, with one-pot reductive amidation of nitroarenes providing a straightforward synthesis approach. To enhance the catalyst stability under reducing conditions, four single-Pd-site catalysts with N, O, P, and I heteroatoms were developed. Among them, the Pd1/NC catalyst achieved excellent ∼100% conversion of nitrobenzene, 90% selectivity for acetanilide, and a turnover frequency (TOF) of 681 h–1, with no obvious decay after six cycles in an autoclave reactor and over 220 h in a fixed-bed durability test. Various substrates further showed the universality for the reductive amidation of nitroaromatics on robust single-Pd-site catalysts. The Pd–N coordination facilitated H2 activation and stabilized the single Pdδ+ ions. In situ DRIFTS and control experiments confirmed a mechanism involving PhNO and PhNH2 intermediates. This work provides valuable insights into the design of highly stable single-Pd-site catalysts for reductive amidation.
Authors
- Siquan Feng (ORCID: https://orcid.org/0000-0003-1367-164X)
- Zheng Rong Jiang (ORCID: https://orcid.org/0000-0003-4297-464X)
- Xingju Li (ORCID: https://orcid.org/0000-0002-1302-1527)
- Yunjie Ding (ORCID: https://orcid.org/0000-0001-8894-9648)
- Bin Li (ORCID: https://orcid.org/0000-0003-3909-3796)
- Xiangen Song
- Qiao Yuan (ORCID: https://orcid.org/0000-0003-2976-8470)
- Yutong Cai (ORCID: https://orcid.org/0000-0002-4850-7148)
- Li Yan
Institutions
- University of Science and Technology of China (CN)
- Dalian Institute of Chemical Physics (CN)
- Chinese Academy of Sciences (CN)
- Institute of Catalysis and Petrochemistry (RU)
- Shanghai Advanced Research Institute (CN)
- Shanghai Institute of Applied Physics (CN)
- Dalian National Laboratory for Clean Energy (CN)
- University of Chinese Academy of Sciences (CN)
- State Key Laboratory of Catalysis
Publication Details
- Journal
- ACS Applied Nano Materials
- Published
- 2025-03-26
- DOI
- https://doi.org/10.1021/acsanm.5c00715
- Citations
- 2
- Primary Topic
- Chemical Synthesis and Analysis
- Type
- article
- Field-Weighted Citation Impact
- 1.61
Funders
- National Natural Science Foundation of China
- Chinese Academy of Sciences
- Dalian Institute of Chemical Physics
- National Key Research and Development Program of China