Highly selective α-aryloxyalkyl C–H functionalisation of aryl alkyl ethers

Bell, Jonathan D. and Robb, Iain and Murphy, John A. (2022) Highly selective α-aryloxyalkyl C–H functionalisation of aryl alkyl ethers. Chemical Science, 13 (43). pp. 12921-12926. ISSN 2041-6520 (https://doi.org/10.1039/D2SC04463C)

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Abstract

We report highly selective photocatalytic functionalisations of alkyl groups in aryl alkyl ethers with a range of electron-poor alkenes using an acridinium catalyst with a phosphate base and irradiation with visible light (456 nm or 390 nm). Experiments indicate that the reaction operates via direct single-electron oxidation of the arene substrate ArOCHRR′ to its radical cation by the excited state organic photocatalyst; this is followed by deprotonation of the ArOC–H in the radical cation to yield the radical ArOC˙RR′. This radical then attacks the electrophile to form an intermediate alkyl radical that is reduced to complete the photocatalytic cycle. The oxidation step is selective for activated arenes (ArOR) over their non-activated counterparts and the subsequent deprotonation of the methoxy group affords the α-aryloxyalkyl radical that leads to a wide range of functionalised products in good to excellent yield.

  • Item type:Article
    ID code:83141
    Dates:
    Date
    Event
    20 October 2022
    Published
    20 October 2022
    Published Online
    15 October 2022
    Accepted
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:09 Nov 2022 16:02
    Last modified:09 Apr 2024 03:40
    URI:https://strathprints.strath.ac.uk/id/eprint/83141
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