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ZrO2 Supported Cu Nanoparticles for Sonogashira and Ullmann Coupling Reactions Under Palladium-Free Conditions

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Abstract

Cu nanoparticles supported on ZrO2 (CuNPs@ZrO2) were synthesized using a one‐step co-precipitation process, and their application in C–C coupling reactions was investigated. The catalyst was characterized using XRD, XPS, SEM, TEM, and TGA techniques. The prepared catalyst was used for the Sonogashira cross-coupling reactions of aryl bromides with phenyl-acetylene in the presence of K2CO3 in DMF at 110 °C, which resulted in substituted alkynes with good to excellent yields. The protocol was also extended for the Ullmann coupling reactions of aryl iodides under similar reaction conditions, yielding the desired products with good to excellent yields without homo-coupling. Interestingly, unlike other copper catalysts, the present catalyst worked under air and did not require an inert atmosphere to prevent alkyne. This catalytic system is versatile, tolerant, and significantly cheaper than the “traditional” Pd-catalyzed Sonogashira cross-coupling of terminal alkynes with aryl halides. The catalyst could be reused for five catalytic cycles with no significant change in the product yield. All of these characteristics make our prepared CuNPs@ZrO2 catalyst quite suitable for the gram-scale synthesis of biaryls and alkynes, with a simple workup.

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Acknowledgements

Seema Patil, is grateful to the Department of Science and Technology (DST), New Delhi, Government of India, for the award of the Women Scientist Scheme-A (WOSA), File no. SR/WOS-A/CS-85/2018. Archana Rajmane is a BARTI-Fellow and grateful to the Government of Maharashtra (India) for the financial support under Dr. Babasaheb Ambedkar National Research Fellowship (BANRF-2020) [BANRF-2020/21-22/850 dated 16/02/2022].

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Authors and Affiliations

  1. Department of Chemistry, Vivekanand College, Kolhapur (Empowered Autonomous), Kolhapur, Maharashtra, India

    Seema P. Patil, Archana S. Rajmane, Vijaya S. Rajmane & Arjun S. Kumbhar

  2. Chemical Engineering and Process Development Division, CSIR—National Chemical Laboratory, Pune, M. S., 411008, India

    Sanjay N. Jadhav & Chandrashekhar V. Rode

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  1. Seema P. Patil
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Correspondence to Arjun S. Kumbhar.

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Patil, S.P., Rajmane, A.S., Jadhav, S.N. et al. ZrO2 Supported Cu Nanoparticles for Sonogashira and Ullmann Coupling Reactions Under Palladium-Free Conditions. Catal Lett 154, 3078–3090 (2024). https://doi.org/10.1007/s10562-023-04513-w

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