Cu(I)-Catalyzed Aminative Aza-Annulation of Enynyl Azide using N-Fluorobenzenesulfonimide: Synthesis of 5-Aminonicotinates

Abstract

An unprecedented copper-catalyzed aminative aza-annulation of enynyl azide using commercially available N-fluorobenzenesulfonimide (NFSI) as an amination reagent is described. The reaction proceeds via regioselective inter-/intramolecular diamination, incorporating one nitrogen from the NFSI and the other from the azide, to provide amino-substituted nicotinate derivatives in a single step with moderate to high yield. This method represents an efficient way to access diverse aminonicotinates through direct C-N bond-coupling processes.

Recent advances in the tandem annulation of 1,3-enynes to functionalized pyridine and pyrrole derivatives

“…Then, the Reddy group developed a copper-catalyzed aminative aza-annulation of enynyl azides with N -fluorobenzenesulfonimide (NFSI) to provide amino-substituted nicotinate derivatives 8 in good to excellent yield ( Scheme 4 ) [ 50 ]. The investigation showed that the electronic effect of the residue R on the substrates influences the results significantly.…”

Copper-catalysed radical reactions of alkenes, alkynes and cyclopropanes with N–F reagents

“…The proposed mechanism was very similar to previous system reported by these authors. 36,43 Based on Li´s findings, Ranjan and co-workers developed a method for the synthesis of amino nicotinates 45 by aminative aza-annulation of enynyl azides using NFSI (Scheme 29a). The reaction took place by regioselective inter-/intramolecular diamination: one nitrogen atom from the NFSI and the other from the azide.…”

(Diacetoxy)iodobenzene-Mediated Regioselective Imidation of Imidazoheterocycles with N-Fluorobenzenesulfonimide

“…NFSI can act as a source of both fluoronium cation for fluorination and nucleophilic nitrogen or nitrogen radical for amination. 14 So far, few groups have explored the transition-metal-catalyzed amination of arenes with NFSI (Scheme 1a). 10 Recently, Pan and co-workers described a copper-catalyzed imidation of heterocycles such as thiophene, furan, and pyrrole with NFSI (Scheme 1b).…”