Dearomative Construction of 2D/3D Frameworks from Quinolines via Nucleophilic Addition/Borate‐Mediated Photocycloaddition

Dearomative construction of multiply‐fused 2D/3D frameworks, composed of aromatic two‐dimensional (2D) rings and saturated three‐dimensional (3D) rings, from readily available quinolines has greatly contributed to drug discovery. However, dearomative cycloadditions of quinolines in the presence of photocatalysts usually afford 5,6,7,8‐tetrahydroquinoline (THQ)‐based polycycles, and dearomative access to 1,2,3,4‐THQ‐based structures remains limited. Herein, we present a chemo‐, regio‐, diastereo‐, and enantioselective dearomative transformation of quinolines into 1,2,3,4‐THQ‐based 6–6–4‐membered rings without any catalyst, through a combination of nucleophilic addition and borate‐mediated [2+2] photocycloaddition. Detailed mechanistic studies revealed that the photoexcited borate complex, generated from quinoline, organolithium, and HB(pin), accelerates the cycloaddition and suppresses the rearomatization that usually occurs in conventional photocycloaddition. Based on our mechanistic analysis, we also developed further photoinduced cycloadditions affording other types of 2D/3D frameworks from isoquinoline and phenanthrene.