Diversification of Naphthol Skeletons Triggered by Aminative Dearomatization

Abstract

A silver-catalyzed aminative dearomatization of naphthols has been developed and integrated into a stepwise approach for subsequent skeletal diversifications including ring expansion, ring opening, ring contraction, and atom transmutation of aryl scaffolds. This approach enables the synthesis of a diverse array of azepinones, unsaturated amides, isoquinolines, and indenones from naphthol substrates. Its application in the synthesis of bioactive and functional molecules as well as the conversion of complex molecular skeletons underscores its broad potential applicability. Mechanistic investigations suggest the intermediacy of the dearomatized intermediates.

Chemoselective silver-catalyzed nitrene transfer: Tunable syntheses of azepines and cyclic carbamimidates

“…5 However, inconsistent selectivity between nitrogen insertion and C(sp 2 )-H amination, coupled with the need for high temperatures, Rh loadings, and prolonged reaction times limited the versatility of this chemistry. Luan and coworkers similarly reported the synthesis of azepinones via the aminative dearomatization of naphthols, 6 although Scheme 1. Previous approaches to azepine synthesis and chemoselective silver-catalyzed dearomative ring expansion.…”

Chemoselective Silver-Catalyzed Nitrene Transfer: Tunable Syntheses of Azepines and Cyclic Carbamimidates

“…However, inconsistent selectivity between nitrogen insertion and C(sp 2 )–H amination, coupled with the need for high temperatures, high Rh loadings, and prolonged reaction time, limited the versatility of this chemistry. Luan and co-workers similarly reported the synthesis of azepinones via the aminative dearomatization of naphthols, although high temperatures and arene functionality at the ortho position were required. The Leonori group reported an elegant synthesis of azepines via a singlet aryl nitrene generated from photolysis of a nitroarene (Scheme C) followed by reduction of the azepines to their respective azepanes .…”