The OCF₃ group is of high interest in the quest for new drugs and agrochemicals, thanks to its atypical features. This Highlight article depicted the recent and impressive advances toward the synthesis of OCF₃-containing molecules.

The synthesis of highly functionalised N-heterocycles has been achieved by the visible light mediated photoredox conversion of tertiary amines to azomethine ylides and their further reaction with maleimide derivatives as dipolarophiles.