Enhancing the performance for palladium catalysed tert-butyl hydroperoxide-mediated Wacker-type oxidation of alkenes

Matthew N. Blair; Meadhbh Murray-Williams; Calum Maguire; Clare L. Brown; Qun Cao; Hongxin Chai; Yitong Li; Róisín L. O'hagan; Paul Dingwall; Panagiotis Manesiotis; Catherine L. Lyall; John P. Lowe; Ulrich Hintermair; Peter C. Knipe; Mark J. Muldoon

doi:10.1039/D3CY01046E

Enhancing the performance for palladium catalysed tert-butyl hydroperoxide-mediated Wacker-type oxidation of alkenes

Matthew N. Blair, Meadhbh Murray-Williams, Calum Maguire, Clare L. Brown, Qun Cao, Hongxin Chai, Yitong Li, Róisín L. O'hagan, Paul Dingwall, Panagiotis Manesiotis, Catherine L. Lyall, John P. Lowe, Ulrich Hintermair, Peter C. Knipe, Mark J. Muldoon

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

2 Citations (SciVal)

Abstract

This work examines the palladium(II) catalysed oxidation of terminal alkenes to their corresponding methyl ketones using tert-butyl hydroperoxide (TBHP) as the oxidant. The study aimed to reduce catalyst loadings and to understand some of the factors which are important in the design of more effective methods. A series of ligands based around 2-(2-pyridyl)benzoxazole (PBO) were studied and a new dicationic catalyst was developed which can operate more efficiently than previously reported catalysts. The choice of solvent system was also found to have a significant impact on catalyst performance. In the case of oct-1-en-3-yl acetate, a model substrate for a challenging class of substrates (protected allylic alcohols), it was found that using 1,1,1,3,3,3-hexafluoroisopropanol (HFIP), as part of a solvent mixture, greatly improved the reaction; enabling shorter reaction times and lower catalyst loadings.

Original language	English
Pages (from-to)	6224-6232
Number of pages	9
Journal	Catalysis Science & Technology
Volume	13
Issue number	21
Early online date	28 Sept 2023
DOIs	https://doi.org/10.1039/D3CY01046E
Publication status	Published - 7 Nov 2023

Bibliographical note

Funding Information:
We thank Conor McGrann and Donal Moran of Queen's University's ASEP Analytical Services for ESI-MS and elemental analysis. For funding, we are grateful to the following: the Department for the Economy (DfE) Northern Ireland for studentships (M. Blair, M. Murray-Williams, C. Maguire), China Scholarship Council (No. 201506030041) (H. Chai) and the EPSRC/Catalysis Hub (EP/R027129/1) for postdoctoral funding (Q. Cao). The Royal Society for a University Research Fellowship (UF160458) (U. Hintermair), and EPSRC for funding the Dynamic Reaction Monitoring Facility at the University of Bath (EP/P001475/1).

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Blair, M. N., Murray-Williams, M., Maguire, C., Brown, C. L., Cao, Q., Chai, H., Li, Y., O'hagan, R. L., Dingwall, P., Manesiotis, P., Lyall, C. L., Lowe, J. P., Hintermair, U., Knipe, P. C., & Muldoon, M. J. (2023). Enhancing the performance for palladium catalysed tert-butyl hydroperoxide-mediated Wacker-type oxidation of alkenes. Catalysis Science & Technology, 13(21), 6224-6232. https://doi.org/10.1039/D3CY01046E

Blair, MN, Murray-Williams, M, Maguire, C, Brown, CL, Cao, Q, Chai, H, Li, Y, O'hagan, RL, Dingwall, P, Manesiotis, P, Lyall, CL , Lowe, JP , Hintermair, U, Knipe, PC & Muldoon, MJ 2023, 'Enhancing the performance for palladium catalysed tert-butyl hydroperoxide-mediated Wacker-type oxidation of alkenes', Catalysis Science & Technology, vol. 13, no. 21, pp. 6224-6232. https://doi.org/10.1039/D3CY01046E

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abstract = "This work examines the palladium(II) catalysed oxidation of terminal alkenes to their corresponding methyl ketones using tert-butyl hydroperoxide (TBHP) as the oxidant. The study aimed to reduce catalyst loadings and to understand some of the factors which are important in the design of more effective methods. A series of ligands based around 2-(2-pyridyl)benzoxazole (PBO) were studied and a new dicationic catalyst was developed which can operate more efficiently than previously reported catalysts. The choice of solvent system was also found to have a significant impact on catalyst performance. In the case of oct-1-en-3-yl acetate, a model substrate for a challenging class of substrates (protected allylic alcohols), it was found that using 1,1,1,3,3,3-hexafluoroisopropanol (HFIP), as part of a solvent mixture, greatly improved the reaction; enabling shorter reaction times and lower catalyst loadings.",

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AU - Cao, Qun

AU - Chai, Hongxin

AU - Li, Yitong

AU - O'hagan, Róisín L.

AU - Dingwall, Paul

AU - Manesiotis, Panagiotis

AU - Lyall, Catherine L.

AU - Lowe, John P.

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AU - Knipe, Peter C.

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N2 - This work examines the palladium(II) catalysed oxidation of terminal alkenes to their corresponding methyl ketones using tert-butyl hydroperoxide (TBHP) as the oxidant. The study aimed to reduce catalyst loadings and to understand some of the factors which are important in the design of more effective methods. A series of ligands based around 2-(2-pyridyl)benzoxazole (PBO) were studied and a new dicationic catalyst was developed which can operate more efficiently than previously reported catalysts. The choice of solvent system was also found to have a significant impact on catalyst performance. In the case of oct-1-en-3-yl acetate, a model substrate for a challenging class of substrates (protected allylic alcohols), it was found that using 1,1,1,3,3,3-hexafluoroisopropanol (HFIP), as part of a solvent mixture, greatly improved the reaction; enabling shorter reaction times and lower catalyst loadings.

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Enhancing the performance for palladium catalysed tert-butyl hydroperoxide-mediated Wacker-type oxidation of alkenes

Abstract

Bibliographical note

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Enhancing the performance for palladium catalysed tert-butyl hydroperoxide-mediated Wacker-type oxidation of alkenes

Abstract

Bibliographical note

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AP19: Developing Catalyst Strategies for a Truly Circular Plastic Economy

An Integrated, Multi-Dimensional In-Operando Reaction Monitoring Facility for Homogenous Catalysis Research

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