Silver salt enabled H/D exchange at the β-position of thiophene rings: synthesis of fully deuterated thiophene derivatives.

We disclose a silver catalyzed H/D exchange reaction, which can introduce the deuterium atom at the β position of thiophene rings without the assistance of any coordinating groups. The advantages of this reaction include operation in open air, usage of DO as the deuterium source, good tolerance to a range of functional groups and obtaining high atom% deuterium incorporation. In addition, this H/D exchange reaction is employed for direct deuteration of a thiophene based monomer, which is usually prepared by multistep synthesis from expensive deuterated starting materials.

Synthesis of Multideuterated (Hetero)aryl Bromides by Ag(I)-Catalyzed H/D Exchange.

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 AgCO as catalyst and DO as deuterium source.

Ag(i)-Mediated hydrogen isotope exchange of mono-fluorinated (hetero)arenes.

An efficient approach to install deuterium into mono-fluorinated (hetero)arenes by a AgCO/Sphos-mediated HIE protocol with DO as the deuterium source has been disclosed. This method showed a specific site selectivity of deuteration at the α-position of the fluorine atom, which is complementary to the existing transition metal-catalyzed HIE process.

AgCO-Catalyzed H/D Exchange of Five-Membered Heteroarenes at Ambient Temperature.

AgCO-catalyzed hydrogen isotope exchange of five-membered heteroarenes is disclosed. The reaction can be conducted in the open air, at ambient temperature, and with DO as deuterium source. Moreover, this protocol showed orthogonal site selectivity to existing technology, thereby greatly expanding the scope of substrates for HIE reaction.