Iridium(III)-Catalyzed Intermolecular Mild N-Arylation of Aliphatic Amides Using Quinoid Carbene: A Migratory Insertion-Based Approach
Satabdi Bera, Saikat Roy, Shyam Chand Pal, Anakuthil Anoop, Rajarshi Samanta
Abstract
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.
Topics & Concepts
ChemistryCatalysisIntermolecular forceDiazoMigratory insertionCarbeneDenticityIridiumSubstrate (aquarium)AzideCombinatorial chemistryInsertion reactionMedicinal chemistryOrganic chemistryMoleculeCrystal structureOceanographyGeologyCyclopropane Reaction MechanismsCatalytic C–H Functionalization MethodsSynthesis and Catalytic Reactions