Rh(III)‐Catalyzed Diverse C—H Functionalization of Iminopyridinium Ylides

Main observation and conclusion Divergent synthesis of useful skeletons has been realized via rhodium(III)‐catalyzed C—H activation of iminopyridinium ylides and coupling with various unsaturated coupling reagents. Isocoumarins and isoquinolones were obtained via cleavage of the C—N or N—N bond in the ylidic directing group, while fluorinated alkenes were delivered with the directing group intact. The reactions occurred with wide substrate scopes and good efficiency under redox‐neutral and air‐tolerant conditions. Representative products exhibit solid‐state fluorescent property and bioactivity of inhibition toward human cancer cells.