Microwave‐Assisted/Pd‐Catalyzed Regioselective Double C‐N Arylations of 1,2,3‐Triiodobenzene: Efficient and Unexpected Synthesis of N1,N2‐Bis(2,3‐diiodoaryl)benzene‐1,2‐diamines

Abstract

ABSTRACTA simple, direct, and regioselective protocol to the synthesis of N1,N2‐bis(2,3‐diiodoaryl)benzene‐1,2‐diamines through highly regioselective microwave‐assisted/palladium‐catalyzed double C‐N arylations of 1,2,3‐triiodobenzene and benzene‐1,2‐diamine is reported. Remarkably, the C‐N arylations proceeded bimolecularly at the terminal positions, the most active and less hindered position. This process was efficient and tolerated a wide range of substrates. The reaction of electron‐rich/neutral 1,2,3‐triiodoarene systems and electron‐rich 1,2‐diamines under the optimized conditions provided the highest isolated yields. This article describes a method for the first and unprecedented synthesis of tetra‐iodinated N1,N2‐diarylbenzene‐1,2‐diamine and iodinated 5,10‐dihydrophenazine products that is regioselective and scalable and provides useful derivatives for other chemical reactions especially in the synthesis of new NHC ligands.