Mechanistic insights into copper-catalyzed aerobic oxidative coupling of N-N bonds.

ABSTRACT: Catalytic N-N coupling is a valuable transformation for chemical synthesis and energy conversion. Here, mechanistic studies are presented for two related copper-catalyzed oxidative aerobic N-N coupling reactions, one involving the synthesis of a pharmaceutically relevant triazole and the other relevant to the oxidative conversion of ammonia to hydrazine. Analysis of catalytic and stoichiometric N-N coupling reactions support an "oxidase"-type catalytic mechanism with two redox half-reactions: (1) aerobic oxidation of a Cu^I catalyst and (2) Cu^II-promoted N-N coupling. Both reactions feature turnover-limiting oxidation of Cu^I by O₂, and this step is inhibited by the N-H substrate(s). The results highlight the unexpected facility of the N-N coupling

SUBMITTER: Ryan MC 

PROVIDER: S-EPMC8146583 | biostudies-literature | 2019 Dec

REPOSITORIES: biostudies-literature