Aerobic Ammoxidation of Cyclic Ketones to Dinitrile Products with Copper-Based Catalysts
Adiponitrile (ADN) has wide applications, especially in the polymer industry. With the substantial and increasing global demand for ADN, effective production of ADN using safe and abundant starting materials is highly desirable but very challenging. Herein, we discovered that CuBr, combined with 1,10-phenanthroline (phen), could effectively promote the ammoxidation reaction of cyclohexanone to ADN with a yield of >99% using aqueous ammonia as the nitrogen source and O<sub>2</sub> as the terminal oxidant under mild reaction conditions (80 °C, 5 atm O<sub>2</sub>). Moreover, cyclic ketones with various carbon numbers and substituent groups could also be converted into the corresponding dinitrile products with high yields. A detailed mechanistic study revealed that the reaction proceeded through a radical-mediated pathway, and the reason for the high selectivity to ADN was discussed. This study offers a new, simple, and cost-effective route to produce ADN and other dinitrile products.
Authors
- Shunhan Jia (ORCID: https://orcid.org/0000-0002-4867-3103)
- Zhanrong Zhang (ORCID: https://orcid.org/0000-0002-1334-9637)
- Qinglei Meng (ORCID: https://orcid.org/0000-0002-7958-3776)
- Huizhen Liu (ORCID: https://orcid.org/0000-0002-6801-7816)
- Bingfeng Chen (ORCID: https://orcid.org/0000-0002-9519-2521)
- Haijun Yang (ORCID: https://orcid.org/0000-0001-8941-7571)
- Qingling Xu (ORCID: https://orcid.org/0000-0003-4333-4214)
- Mingyang Liu (ORCID: https://orcid.org/0000-0002-6643-5096)
- Wen‐Li Yuan
- Ziwei Zhao (ORCID: https://orcid.org/0009-0003-7403-1715)
- Pei Zhang (ORCID: https://orcid.org/0000-0001-9447-9216)
- Buxing Han (ORCID: https://orcid.org/0000-0003-0440-809X)
- Ying Wang (ORCID: https://orcid.org/0000-0002-5407-2443)
Institutions
- Chinese Academy of Sciences (CN)
- Beijing National Laboratory for Molecular Sciences (CN)
- Green Chemistry (PL)
- University of Chinese Academy of Sciences (CN)
- East China Normal University (CN)
Publication Details
- Journal
- Journal of the American Chemical Society
- Published
- 2024-12-19
- DOI
- https://doi.org/10.1021/jacs.4c14875
- Citations
- 4
- Primary Topic
- Chemical Synthesis and Reactions
- Type
- article
- Field-Weighted Citation Impact
- 1.00
Funders
- National Natural Science Foundation of China
- Chinese Academy of Sciences
- Youth Innovation Promotion Association of the Chinese Academy of Sciences
- University of Chinese Academy of Sciences
- Institute of Chemistry, Chinese Academy of Sciences
- National Key Research and Development Program of China
- Youth Innovation Promotion Association
- Beijing National Laboratory for Molecular Sciences