Dearomative cycloaddition reactions represent an ideal means of converting flat arenes into three-dimensional architectures of increasing interest in medicinal chemistry. Quinolines, isoquinolines, and quinazolines, despite containing latent diene and alkene subunits, are scarcely applied in cycloaddition reactions because of the inherent low reactivity of aromatic systems and selectivity challenges. Here, we disclose an energy transfer–mediated, highly regio- and diastereoselective intermolecular [4 + 2] dearomative cycloaddition reaction of these bicyclic azaarenes with a plethora of electronically diverse alkenes. This approach bypasses the general reactivity and selectivity issues, thereby providing various bridged polycycles that previously have been inaccessible or required elaborate synthetic efforts. Computational studies with density functional theory elucidate the mechanism and origins of the observed regio- and diastereoselectivities.

脱芳环加成反应是将平面芳烃转化为三维结构的理想方法，这在药物化学中日益受到关注。喹啉、异喹啉和喹唑啉尽管含有潜在的二烯和烯烃亚基，但由于芳族体系固有的低反应性和选择性挑战，很少应用于环加成反应。在这里，我们公开了这些双环氮杂芳烃与大量电子不同的烯烃的能量转移介导的、高度区域和非对映选择性的分子间[4 + 2]脱芳香环加成反应。这种方法绕过了一般的反应性和选择性问题，从而提供了以前无法获得或需要精心合成的各种桥连多环。密度泛函理论的计算研究阐明了观察到的区域选择性和非对映选择性的机制和起源。