Environmentally Benign Transamidation Protocol for Weakly Nucleophilic Aromatic Amines with N‐Acyl‐2‐piperidinones: Catalyst‐, Additive‐, Base‐ and Solvent‐Free Condition

Abstract

Transamidation of weakly nucleophilic aromatic amines is achieved under melt conditions and in absence of catalyst, activating agent, base, and solvent. Chemoselectivity of the protocol is demonstrated with transamidation of aniline‐bearing protic carboxylic acid group and wide range of anilines. Broad applicability of the process is demonstrated with the synthesis of bioactive natural product amide, Avenanthranamide‐A. By‐product was isolated for re‐use in synthesis of starting amide, manifests atom economy, and sustainability of the protocol. Thus, our findings imply that the developed protocol is environmentally benign, operationally simple yet versatile for protection‐deprotection free synthesis of amides, peptides and amide‐based drugs.

Ring Opening of N-Acyl Lactams Using Nickel-Catalyzed Transamidation

“…This strategic approach involves the introduction of new substituents by inducing the dissociation of carbon–nitrogen bonds in amides through the manipulation of the steric and electronic attributes of the amide skeleton, thereby leading to the perturbation of their resonance stability . While investigations into methods involving transition metal catalysts are ongoing, interesting findings pertaining to reactions conducted without transition metal catalysts have also been reported …”