Recent Advances in Molecule Synthesis Involving C-C Bond Cleavage of Ketoxime Esters

The synthetic strategies of oxime derivatives participating in radical-type reactions have been rapidly developed in the last few decades. Among them, the N-O bond cleavage of oxime esters leading to formation of nitrogen-centered radicals triggers adjacent C-C bond cleavage to produce carbon-centered free radicals, which has been virtually used in organic synthesis in recent years. Herein, we summarized the radical reactions involving oxime N-O bond and C-C bond cleavage through this special reaction form, including those from acyl oxime ester derivatives and cyclic ketoxime ester derivatives. These contents were systematically classified according to different reaction types. In this review, the free radical reactions involving acyl oxime esters and cyclic ketoxime esters after 2021 were included, with emphasis on the substrate scope and reaction mechanism.

Automated summary

The synthetic strategies of oxime derivatives participating in radical-type reactions have been rapidly developed in the last few decades. The N-O bond cleavage of oxime esters leading to the formation of nitrogen-centered radicals triggers adjacent C-C bond cleavage to produce carbon-centered free radicals, which has been virtually used in organic synthesis in recent years. In this review, the free radical reactions involving acyl oxime esters and cyclic ketoxime esters after 2021 were included, with emphasis on the substrate scope and reaction mechanism.