Copper cocatalyst modulated radical generation for selective heterogeneous photosynthesis of α‑haloketones

Han, Feiyu, Zhang, Dongsheng, Salli, Sofia, Ye, Jiani, Li, Yongwang, Rosei, Federico, Wen, Xiao-Dong, Niemantsverdriet, Hans, Richards, Emma ORCID: https://orcid.org/0000-0001-6691-2377 and Su, Ren 2023. Copper cocatalyst modulated radical generation for selective heterogeneous photosynthesis of α‑haloketones. ACS Catalysis 13 (1) , pp. 248-255. 10.1021/acscatal.2c05189

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Abstract

The α-haloketones are important precursors for synthetic chemistry and pharmaceutical applications; however, their production relies heavily on traditional synthetic methods via halogenation of ketones that are toxic and environmentally risky. Here, we report a heterogeneous photosynthetic strategy of α-haloketone production from aromatic olefins using copper-modified graphitic carbon nitride (Cu–C3N4) under mild reaction conditions. By employing NiX2 (X = Cl, Br) as the halogen source, a series of α-haloketones can be synthesized using atmospheric air as the oxidant under visible-light irradiation. In comparison with pristine carbon nitride, the addition of Cu as a cocatalyst provides a moderate generation rate of halogen radicals and selective reduction of molecular oxygen into •OOH radicals, thus leading to a high selectivity to α-haloketones. The Cu–C3N4 also exhibits high stability and versatility, rendering it a promising candidate for solar-driven synthetic applications.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Additional Information:	License information from Publisher: LICENSE 1: URL: https://creativecommons.org/licenses/by/4.0/, Start Date: 2022-12-15
Publisher:	American Chemical Society
ISSN:	2155-5435
Funders:	EPSRC
Date of First Compliant Deposit:	10 January 2023
Date of Acceptance:	28 November 2022
Last Modified:	14 Jun 2023 16:34
URI:	https://orca.cardiff.ac.uk/id/eprint/155608

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