Recent Advances in Copper-Catalysed Hydrolysis of Aryl Halides to Phenols

Authors

  • Yuehan Li Department of Chemical and Environmental Engineering, University of Nottingham, Ningbo, China

DOI:

https://doi.org/10.54097/h2yah472

Keywords:

Copper catalysis; hydrolysis; aryl halides; phenols; ligand design.

Abstract

Phenol and its derivatives are indispensable bulk and fine-chemical intermediates, widely used in the synthesis of pharmaceuticals, agrochemicals, polymeric materials, dyes, and a broad range of specialty chemicals [1, 2]. Conventional manufacturing routes to phenols generally suffer from multistep operations, harsh conditions, high energy consumption, substantial environmental burdens, and safety concerns [3, 4]. In recent years, the direct hydrolysis of aryl halides to phenols under transition-metal catalysis has attracted considerable attention owing to its step and atom economy as well as its potential environmental benefits [5, 6]. Among various metals, copper has emerged as a focal point because of its low cost, relatively low toxicity, diverse accessible oxidation states, and flexible catalytic pathways [7, 8]. With the rational design of novel ligands and additives, the growing use of greener media, and breakthroughs in nanocatalysis and single-atom catalysis, copper-catalysed hydrolysis has been realised under increasingly mild conditions, with continuously expanding substrate scope, enhanced functional-group tolerance, and improved catalytic efficiency and selectivity [9, 10]. This review provides a systematic summary of research progress in copper-catalysed hydrolysis of aryl halides to phenols, with emphasis on mechanistic understanding, the key components of catalytic systems, and optimisation of reaction conditions, followed by a perspective on current challenges and future directions.

Downloads

Download data is not yet available.

References

[1] Rappoport, Z. (Ed.). (2003). The Chemistry of Phenols. Wiley-VCH.

[2] Ullmann’s Encyclopedia of Industrial Chemistry. Phenols and Cresols. Wiley-VCH, 2012. https://doi.org/10.1002/14356007.a19_299.pub2.

[3] Schmidt, R. J. (2005). Industrial catalytic processes—Phenol production. Applied Catalysis A: General, 280, 89–103. https://doi.org/10.1016/j.apcata.2004.08.030.

[4] Sheldon, R. A. (2016). The E factor 25 years on: The rise of green chemistry. Green Chemistry, 18, 3180–3183. https://doi.org/10.1039/C6GC00611A.

[5] Hartwig, J. F. (2008). Carbon–heteroatom bond formation catalysed by organometallic complexes. Nature, 455, 314–322. https://doi.org/10.1038/nature07369.

[6] Xia, N.; Taillefer, M.; Xia, C. (2016). Efficient copper-catalyzed hydroxylation of aryl chlorides promoted by BHMPO ligand. Angewandte Chemie International Edition, 55, 4606–4609. https://doi.org/10.1002/anie.201600123.

[7] Evano, G.; Blanchard, N.; Toumi, M. (2008). Copper-mediated coupling reactions and their applications. Chemical Reviews, 108, 3054–3131. https://doi.org/10.1021/cr8002505.

[8] Beletskaya, I. P.; Cheprakov, A. V. (2004). Copper in cross-coupling reactions: The post-Ullmann chemistry. Coordination Chemistry Reviews, 248, 2337–2364. https://doi.org/10.1016/j.ccr.2004.09.014

[9] Mehmood, A.; Leadbeater, N. E. (2012). Microwave-promoted copper-catalyzed hydroxylation of aryl halides in water. Green Chemistry, 14, 338–343. https://doi.org/10.1039/C1GC16085K.

[10] Hao, L.; Zhang, Z.; Li, Y. (2020). Atomically dispersed Cu–ZnO–ZrO₂ catalysts for selective hydroxylation of aryl iodides. ACS Catalysis, 10, 1899–1907. https://doi.org/10.1021/acscatal.9b04567.

[11] Anastas, P. T.; Warner, J. C. (1998). Green Chemistry: Theory and Practice. Oxford University Press.

[12] Jutand, A. (2008). Mechanisms of copper-catalyzed coupling reactions. Chemical Reviews, 108, 2300–2347. https://doi.org/10.1021/cr068451h.

[13] Yang, D.; Chen, Y. C.; Zhu, N. (2011). CuI nanoparticle-catalyzed hydroxylation and etherification of aryl halides. Journal of the American Chemical Society, 133, 3622–3625. https://doi.org/10.1021/ja110987a.

[14] Xia, S.; Gan, L.; Wang, K.; Li, Z.; Ma, D. (2016). Copper-Catalyzed Hydroxylation of (Hetero)aryl Halides under Mild Conditions. Journal of the American Chemical Society, 138(41), 13493–13496. https://doi.org/10.1021/jacs.6b08114.

[15] Kochi, J. K. (2002). Journal of Organometallic Chemistry, 653, 11–19. https://doi.org/10.1016/S0022-328X(02)01265-2.

[16] Taillefer, M.; Monnier, F. (2014). Copper-catalyzed C–O and C–N bond formation. Accounts of Chemical Research, 47(10), 2813–2822. https://doi.org/10.1021/ar500202g.

[17] Liang, X.; Li, J.; Chen, Y. (2018). Natural product-derived ligands for copper-catalyzed hydroxylation of aryl halides in aqueous ethanol. Organic Letters, 20, 3204–3208. https://doi.org/10.1021/acs.orglett.8b01234.

[18] Wang, Y.; Zhou, C.; Wang, R. (2015). Copper-catalyzed hydroxylation of aryl halides: efficient synthesis of phenols, alkyl aryl ethers and benzofuran derivatives in neat water. Green Chemistry, 17, 3910. https://doi.org/10.1039/C5GC00871A.

[19] Zhou, X.; Chen, W.; Xu, L. (2017). Cu₂O nanocatalysts for efficient hydroxylation of aryl halides in aqueous media. Catalysis Science & Technology, 7, 2768–2775. https://doi.org/10.1039/C7CY00524E.

Downloads

Published

22-08-2026

How to Cite

Li, Y. (2026). Recent Advances in Copper-Catalysed Hydrolysis of Aryl Halides to Phenols. Highlights in Science, Engineering and Technology, 165, 10-14. https://doi.org/10.54097/h2yah472