Polysubstituted 2-Aminopyrrole Synthesis via Gold-Catalyzed Intermolecular Nitrene Transfer from Vinyl Azide to Ynamide: Reaction Scope and Mechanistic Insights

Abstract

A gold-catalyzed intermolecular reaction of vinyl azides and ynamides is described. This process presents an efficient and mild approach to multisubstituted 2-aminopyrroles in good-to-excellent yields. Control experiments were carried out to distinguish the reactivity between vinyl azides and the corresponding 2H-azirines. A plausible reaction mechanism was also proposed according to previous reports and our preliminary mechanistic studies.

Gold‐Catalyzed Synthesis of Quinolines from Propargyl Silyl Ethers and Anthranils through the Umpolung of a Gold Carbene Carbon

“…For instance, a gold‐catalyzed intermolecular reaction of iminopyridinium ylides and ynamides, reported by Davies and co‐workers, delivers polysubstituted oxazoles in high efficiency. The groups of Ye, Liu, and Huang, have each achieved gold‐catalyzed syntheses of 2‐aminopyrroles using isoxazoles or 2 H ‐azirines as nitrene precursors. Recently, we contributed a gold‐catalyzed C−H annulation of anthranils with alkynes for the expedient assembly of 7‐acylindolyl skeletons by using the potential of anthranil to act as a binucleophile (Scheme , upper part).…”

Gold-catalyzed intermolecular reaction of ynamides with 3-indolyl azides via an unexpected 1,2-alkyl migration

“…Recently, the generation of a-imino gold carbenes [14][15][16][17][18][19][20][21][22] through gold-catalyzed alkyne amination has gained significant attention, because this strategy offers easy access to a variety of valuable complex nitrogen-containing molecules [23][24][25][26][27][28][29][30][31][32][33]. In our recent study on the ynamide chemistry [34][35][36][37][38][39][40][41][42][43][44][45][46][47][48], we first disclosed that benzyl azides could serve as efficient nitrene transfer reagents to react with ynamides for the intermolecular generation of aimino gold carbenes.…”

Gold‐katalysierte Synthese von Chinolinen aus Propargylsilylethern und Anthranilen über die Umpolung eines Goldcarben‐Kohlenstoffatoms

“…Beispielsweise liefert die von Davies und Mitarbeitern publizierte, Gold‐katalysierte intermolekulare Reaktion von Iminopyridiniumyliden und Inamiden mit hoher Effizienz polysubstituierte Oxazole. Den Arbeitsgruppen von Ye, Liu und Huang, gelang jeweils die Gold‐katalysierte Synthese von 2‐Aminopyrrolen aus Isoxazolen oder 2 H ‐Azirinen als Nitren‐Vorstufen. Kürzlich berichteten wir über eine Gold‐katalysierte C‐H‐Anellierung von Anthranilen mit Alkinen für den raschen Aufbau von 7‐Acylindolyl‐Gerüsten durch die Nutzung der Eigenschaft von Anthranil, als potentielles Binukleophil zu agieren (Schema , oberer Teil).…”