Decarboxylative ipso Amination of Activated Benzoic Acids

Up in the air: An oxidative decarboxylative coupling of benzoic acids with unprotected amines has been achieved using bimetallic Pd/Cu catalysis. This simple aniline synthesis only requires air or NMO as an oxidant, is amenable to multigram scale, and allows orthogonality to traditional Pd‐catalyzed cross‐couplings. Mechanistic investigations suggest the intermediacy of a hypervalent Pd species.

Abstract

In the presence of a bimetallic Pd/Cu system with 1,10‐phenanthroline as the ligand and either air or N‐methylmorpholine N‐oxide as the oxidant, electron‐deficient benzoic acids undergo oxidative decarboxylative coupling with unprotected amines. This operationally simple aniline synthesis is widely applicable with respect to the amine and gives good yields, even on multigram scale. The orthogonality of this reaction to other Pd‐catalyzed cross‐couplings allows the concise synthesis of multisubstituted arenes by sequential C−C, C−Cl, and C−N functionalizations. Mechanistic investigations suggest the intermediacy of a hypervalent Pd species.

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