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A novel rearrangement of cycloketoxime esters to cyano-containing benzoates beyond the traditional Beckmann and Neber rearrangement process has been established in the presence of photocatalysis catalysis. This SET-induced structural reorganization of cycloketoxime esters is perfectly an atom economic process and distinguished by mild and safe reaction conditions that avoid acid, base and toxic cyanide salts.

Graphical abstract: Photoinduced fragmentation-rearrangement sequence of cycloketoxime esters

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