Highly efficient catalytic production of oximes from ketones using in situ-generated H2O2

Richard J. Lewis; Kenji Ueura; Xi Liu; Yukimasa Fukuta; Thomas E. Davies; David J. Morgan; Liwei Chen; Jizhen Qi; James Singleton; Jennifer K. Edwards; Simon J. Freakley; Christopher J. Kiely; Yasushi Yamamoto; Graham J. Hutchings

doi:10.1126/science.abl4822

Highly efficient catalytic production of oximes from ketones using in situ-generated H₂O₂

Richard J. Lewis, Kenji Ueura, Xi Liu, Yukimasa Fukuta, Thomas E. Davies, David J. Morgan, Liwei Chen, Jizhen Qi, James Singleton, Jennifer K. Edwards, Simon J. Freakley, Christopher J. Kiely, Yasushi Yamamoto, Graham J. Hutchings

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

141 Citations (SciVal)

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Abstract

The ammoximation of cyclohexanone using preformed hydrogen peroxide (H2O2) is currently applied commercially to produce cyclohexanone oxime, an important feedstock in nylon-6 production. We demonstrate that by using supported gold-palladium (AuPd) alloyed nanoparticles in conjunction with a titanium silicate-1 (TS-1) catalyst, H2O2 can be generated in situ as needed, producing cyclohexanone oxime with >95% selectivity, comparable to the current industrial route. The ammoximation of several additional simple ketones is also demonstrated. Our approach eliminates the need to transport and store highly concentrated, stabilized H2O2, potentially achieving substantial environmental and economic savings. This approach could form the basis of an alternative route to numerous chemical transformations that are currently dependent on a combination of preformed H2O2 and TS-1, while allowing for considerable process intensification.

Original language	English
Pages (from-to)	615-620
Number of pages	6
Journal	Science (New York, N.Y.)
Volume	376
Issue number	6593
DOIs	https://doi.org/10.1126/science.abl4822
Publication status	Published - 5 May 2022

Bibliographical note

Funding Information:
The authors thank UBE Corporation for financial support. XPS data collection was performed at the EPSRC National Facility for XPS (“HarwellXPS”), operated by Cardiff University and UCL, under contract PR16195. R.J.L. and G.J.H. gratefully acknowledge Cardiff University and the Max Planck Centre for Fundamental Heterogeneous Catalysis (FUNCAT) for financial support. X.L. acknowledges financial support from the National Natural Science Foundation of China (22872163 and 22072090). L.C. acknowledges financial support from the National Natural Science Foundation of China (21991153). In addition, S.J.F. acknowledges the award of a Prize Research Fellowship from the University of Bath.

Data and materials availability:
The data supporting the findings of this study are available within the article and its supplementary materials or from the authors upon reasonable request, with the underlying data found at the Cardiff University Data Repository (38).

ASJC Scopus subject areas

General

Access to Document

10.1126/science.abl4822

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This is the author’s version of the work. It is posted here by permission of the AAAS for personal use, not for redistribution. The definitive version was published in Science in Vol 376 on 5/5/2022, https://doi.org/10.1126/science.abl4822
Accepted author manuscript, 188 KB
Supplementary Materials_clean
This is the author’s version of the work. It is posted here by permission of the AAAS for personal use, not for redistribution. The definitive version was published in Science in Vol 376 on 5/5/2022, https://doi.org/10.1126/science.abl4822
Accepted author manuscript, 3.69 MB

Cite this

Lewis, R. J., Ueura, K., Liu, X., Fukuta, Y., Davies, T. E., Morgan, D. J., Chen, L., Qi, J., Singleton, J., Edwards, J. K., Freakley, S. J., Kiely, C. J., Yamamoto, Y., & Hutchings, G. J. (2022). Highly efficient catalytic production of oximes from ketones using in situ-generated H₂O₂. Science (New York, N.Y.), 376(6593), 615-620. https://doi.org/10.1126/science.abl4822

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abstract = "The ammoximation of cyclohexanone using preformed hydrogen peroxide (H2O2) is currently applied commercially to produce cyclohexanone oxime, an important feedstock in nylon-6 production. We demonstrate that by using supported gold-palladium (AuPd) alloyed nanoparticles in conjunction with a titanium silicate-1 (TS-1) catalyst, H2O2 can be generated in situ as needed, producing cyclohexanone oxime with >95% selectivity, comparable to the current industrial route. The ammoximation of several additional simple ketones is also demonstrated. Our approach eliminates the need to transport and store highly concentrated, stabilized H2O2, potentially achieving substantial environmental and economic savings. This approach could form the basis of an alternative route to numerous chemical transformations that are currently dependent on a combination of preformed H2O2 and TS-1, while allowing for considerable process intensification.",

author = "Lewis, {Richard J.} and Kenji Ueura and Xi Liu and Yukimasa Fukuta and Davies, {Thomas E.} and Morgan, {David J.} and Liwei Chen and Jizhen Qi and James Singleton and Edwards, {Jennifer K.} and Freakley, {Simon J.} and Kiely, {Christopher J.} and Yasushi Yamamoto and Hutchings, {Graham J.}",

note = "Funding Information: The authors thank UBE Corporation for financial support. XPS data collection was performed at the EPSRC National Facility for XPS (“HarwellXPS”), operated by Cardiff University and UCL, under contract PR16195. R.J.L. and G.J.H. gratefully acknowledge Cardiff University and the Max Planck Centre for Fundamental Heterogeneous Catalysis (FUNCAT) for financial support. X.L. acknowledges financial support from the National Natural Science Foundation of China (22872163 and 22072090). L.C. acknowledges financial support from the National Natural Science Foundation of China (21991153). In addition, S.J.F. acknowledges the award of a Prize Research Fellowship from the University of Bath. Data and materials availability: The data supporting the findings of this study are available within the article and its supplementary materials or from the authors upon reasonable request, with the underlying data found at the Cardiff University Data Repository (38). ",

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AU - Ueura, Kenji

AU - Liu, Xi

AU - Fukuta, Yukimasa

AU - Davies, Thomas E.

AU - Morgan, David J.

AU - Chen, Liwei

AU - Qi, Jizhen

AU - Singleton, James

AU - Edwards, Jennifer K.

AU - Freakley, Simon J.

AU - Kiely, Christopher J.

AU - Yamamoto, Yasushi

AU - Hutchings, Graham J.

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