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

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 ArOCRR '. 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 alpha-aryloxyalkyl radical that leads to a wide range of functionalised products in good to excellent yield.

Automated summary

Highly selective photocatalytic functionalisations of alkyl groups in aryl alkyl ethers have been achieved using a phosphate-based acridinium catalyst and visible light irradiation. The reaction proceeds through direct single-electron oxidation and subsequent deprotonation steps, resulting in a wide range of functionalised products in good to excellent yield.