Site‐Selective C–H Amidation of 2‐Aryl Quinazolinones Using Nitrene Surrogates

The site‐selective modifications of quinazolinones constitute a pivotal topic in drug discovery and material science. Herein, we describe the rhodium(III)‐catalyzed C–H amidation of 2‐aryl quinazolin‐4(3H)‐ones with a range of nitrene surrogates including dioxazolones, organic azides, and N‐methoxyamides. Complete site‐selectivity and functional group tolerance are observed. Notably, the large‐scale reaction and late‐stage functionalization highlight the synthetic potential of the developed protocol. Combined mechanistic investigations elucidate a plausible reaction mechanism of this process. The site‐selective C–H amidation of 2‐aryl quinazolin‐4(3H)‐ones with dioxazolones under rhodium(III) catalysis is described. Gram‐scale reaction, late‐stage C–H functionalization, and synthetic transformations highlight the potential of the developed method.