Direct carboxylation of aryl tosylates by CO₂ Catalyzed by In situ-generated Ni⁰

A novel Ni0‐catalyzed carboxylation of aryl tosylates with carbon dioxide has been achieved under moderate temperatures and atmospheric pressure. In this procedure, the active Ni0 species is generated in situ by simply mixing the Ni0 precatalyst [NiBr2(bipy)] with an excess of manganese metal. This approach requires neither a glove‐box nor the tedious preparation of sophisticated intermediate organometallic derivatives. This mild, convenient, and user‐friendly process is successfully applied to the valorization of carbon dioxide and the synthesis of versatile reactants with broad tolerance of substituents