Deterium-labeled (hetero)­aryl bromide is one of the most widespread applicable motifs to achieve important deuterated architectures for various scientific applications. Traditionally, these deterium-labeled (hetero)­aryl bromides are commonly prepared via multistep syntheses. Herein, we disclose a direct H/D exchange protocol for deuteration of (hetero)­aryl bromides using Ag2CO3 as catalyst and D2O as deuterium source. This protocol is highly efficient, simply manipulated, and appliable for deuterium-labeling of over 55 (hetero)­aryl bromides including bioactive druglike molecules and key intermediates of functional materials. In addition, this method showed distinguishing site-selectivity toward the existing transition-metal-catalyzed HIE process, leading to multideuterated (hetero)­aryl bromides in one step.

Ag2CO3-catalyzed hydrogen isotope exchange of five-membered heteroarenes is disclosed. The reaction can be conducted in the open air, at ambient temperature, and with D2O as deuterium source. Moreover, this protocol showed orthogonal site selectivity to existing technology, thereby greatly expanding the scope of substrates for HIE reaction. The mechanistic study indicated that the carbonate group plays a crucial role to achieve high levels of deuterium incorporation by lowering the activation energy of H/D exchange process.

An efficient approach for synthesizing congested deuterium-labeled arenes via cascade alkylation and deuteration with aryl iodides has been disclosed.