Iridium(III)-Catalyzed Intermolecular Mild N-Arylation of Aliphatic Amides Using Quinoid Carbene: A Migratory Insertion-Based Approach

An efficient Ir(III)-catalyzed straightforward intermolecular N-arylation of acyclic aliphatic amides has been achieved using quinone diazide as a coupling partner. The reaction has been developed under simple and mild reaction conditions with a broad substrate scope. The bidentate picolinamide group is essential for successful transformation. Mechanistic studies and DFT calculations highlighted the migratory insertion-based pathway. The developed method exhibits different reactivities compared to the reactions of acyclic aliphatic amides using related diazo/azide congeners under Rh(III)/Ir(III) catalysis.

Automated summary

This study demonstrates an efficient Ir(III)-catalyzed straightforward intermolecular N-arylation of acyclic aliphatic amides using quinone diazide as a coupling partner. The reaction conditions are simple and mild with a broad substrate scope, and the bidentate picolinamide group is essential for successful transformation. Mechanistic studies and DFT calculations highlight a migratory insertion-based pathway. The developed method exhibits different reactivities compared to reactions using related diazo/azide congeners under Rh(III)/Ir(III) catalysis.