Dual Activation of Enals and γ‐C(sp³)‐H Bond of <i>p</i>‐Quinols for the Synthesis of Naphthylamines via Cyclization/Dual Aromatization

Comprehensive Summary The synthesis of fused arenes from non‐aromatic precursors is useful but challenging. Herein, the synthesis of widely‐used naphthylamines was focused. The three‐component reactions of p ‐quinols, enals and amines were investigated under the dienamine/iminium‐ based dual organocatalysis. The efficient synthesis of naphthylamines was achieved via a formal [3+3] cyclization of the amines activated p ‐quinols and enals, with the following Bu 4 NOAc/AgNO 3 facilitated dual aromatization. The different reactivity of in‐situ generated dienamine and iminium intermediates resulted in the differentiating catalysis, providing an efficient and practical methodology for the synthesis of fused arenes from non‐aromatic precursors.