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We report an efficient photocatalytic strategy for direct oxime etherification of unactivated C(sp3)-H bonds through hydrogen atom transfer (HAT) activation, employing low loading FeCl3 as catalyst under blue light irradiation. This methodology demonstrates a broad substrates scope with excellent functional group tolerence, including cycloalkanes, ethers, amides, sulfonamides, phosphoramides, and ketones. Furthermore, the reaction system exhibits remarkable scalability through continuous flow photoreactor, achieving practical gram-scale production of pharmaceutically relevant oxime ether derivatives with improved yields.