Formal C−H Carboxylation of Unactivated Arenes

Abstract

A formal C−H carboxylation of unactivated arenes using CO ₂ in green solvents is described. The present strategy combines a sterically controlled Ir‐catalyzed C−H borylation followed by a Cu‐catalyzed carboxylation of the in situ generated organoboronates. The reaction is highly regioselective for the C−H carboxylation of 1,3‐disubstituted and 1,2,3‐trisubstituted benzenes, 1,2‐ or 1,4‐symmetrically substituted benzenes, fluorinated benzenes and different heterocycles. The developed methodology was applied to the late‐stage C−H carboxylation of commercial drugs and ligands.

Abstract

Late‐stage carboxylation: Regioselective C−H carboxylation of unactivated arenes is now possible. C−H carboxylation can be realized in green solvents and can be used for the late‐stage carboxylation of practically valuable molecules.