Nickel-Catalyzed Deuteroalkylation Using Thianthrenium Salts

Isotopically labeled compounds are essential both in organic and pharmaceutical chemistry. The standard synthetic method of such molecules often involves the utilization of deuterated building blocks, allowing functional groups and the incorporation of deuterium into the target molecule in a one step. Herein, taking D2O as a cheap deuterium source, we highlight our approach to access various α-deuterated alkyl thianthrenium (TT) salts via a pH-dependent hydrogen isotope exchange (HIE) process. Through the in situ formation of isotopically labeled alkyl halides these TT salts exhibit exceptional compatibility in a range of nickel-catalyzed hydrodeuteroalkylation of unactivated olefins and nickel-catalyzed cross-electrophile coupling reactions with alkyl, alkenyl and (hetero)aryl bromides. This technique proves to be invaluable accessing a range of deuterium-labeled compounds, particularly those of pharmaceutical significance.