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

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.

Photocatalytic C–N bond construction toward high-value nitrogenous chemicals

“…These compounds have been used to construct N-containing compounds. [91][92][93][94] The previous catalytic methods (e.g., thermocatalysis and electrocatalysis) have made (c) A phosphine-mediated dual catalytic system is composed of a photoredox catalytic cycle and a cobalt catalytic cycle. The photoredox catalytic cycle absorbs light and excites the activator (e.g., phosphine), while the cobalt catalytic cycle activates the photoredox catalytic cycle and abstracts electrons to generate acyl cations to promote the reaction toward the amide formation.…”

“…These compounds have been used to construct N-containing compounds. 91–94 The previous catalytic methods ( e.g. , thermocatalysis and electrocatalysis) have made great advancements in the catalytic activation of C–O/N–O bonds to form C–N bonds.…”

Copper-Catalyzed 1,2-Difunctionalization Trifluoromethylamidation of Alkynes Assisted by a Coordinating Group

“…In recent years, bidentate directing groups have been demonstrated as an efficient and novel tool in C–H or N–H bond functionalization chemistry . The theory of using such groups arose in order to tune the coordinating ability of the transition metal center and chelation system.…”

Rh(II)-Catalyzed Synthesis of N-Aryl 2-pyridone Using 2-Oxypyridine and Diazonaphthoquinone Via 1,6-Benzoyl Migratory Rearrangement

“…Though significant progress has been realized in the C–H bond arylations utilizing quinoid carbene generated from diazonaphthoquinone precursors, there is a limited report in NH-arylations via NH insertion to quinoid carbene (Scheme b) . Very recently, our group developed an N -arylation of the amide center using migratory insertion of quinoid carbene, generated from diazonaphthoquinone . Additionally, we also developed 2-pyridone N -naphthylation using an internal alkyne as a coupling partner .…”