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DOI: 10.1055/s-0043-1775477
Cumene-to-Phenol Process Mediated by Bromine Radicals through Photoinduced Ligand-to-Metal Charge Transfer
This research was supported in part by Cornell University and Princeton University. This research is supported in part by the Department of Energy, Office of Science, Office of Basic Energy Sciences, Catalysis Science Early Career Award (DE-SC0024412). This research made use of the NMR Facility at Cornell University, supported by National Science Foundation (CHE-1531632) and the Cornell Center for Materials Research Facilities, supported by National Science Foundation (DMR-1719875).
Abstract
Selective C–H activation via hydrogen atom transfer (HAT) has gained significant interest recently. One industrial application for HAT can be found in the tertiary benzylic C–H bond of cumene for producing phenol, a versatile chemical feedstock for various industries. However, the overall phenol yield remains low using the existing Hock process due to the poor selectivity towards the key reaction intermediate, cumene hydroperoxide (CHP). Here, we demonstrate an efficient strategy for phenol production through photooxidation of cumene to CHP using iron bromide under blue light irradiation, where bromine radicals (generated in situ via ligand-to-metal charge transfer) are used as hydrogen atom abstractors. Mechanistic studies revealed the cumene-to-CHP conversion occurred via a tertiary C–H bond abstraction by a radical mechanism, and the acetic acid and water additives increased CHP selectivity through stabilizing peroxides. The cumene-phenol process achieved up to 88% yield of CHP in 1 hour and could be used with a wide range of substrates. We thus developed a selective, mild, and efficient phenol production method using iron bromide under photooxidative conditions.
Key words
HAT - selective oxidation - photochemistry - cumene - ligand-to-metal charge transfer - bromine radical - phenol process - Hock rearrangementSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0043-1775477. Experimental details, methods, data, spectra, and photographs of the experimental setup are included.
- Supporting Information
Publication History
Received: 17 February 2025
Accepted after revision: 31 March 2025
Article published online:
16 May 2025
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