Designing and Accurately Developing a [6 + 2] Dipolar Cycloaddition for the Synthesis of Benzodiazocines

1,6-Dipolar cycloadditions represent a valuable strategy for the rapid construction of medium-sized rings. Herein, we describe the concept for the design of 1,6-dipoles that bypasses the regioselectivity. Through the introduction of an amino group into Morita–Baylis–Hillman (MBH) carbonates, unprecedented [6 + 2] dipolar cycloadditions were accurately developed with Cs2CO3, efficiently delivering a series of benzodiazocines in mild conditions. Computational studies bring a deeper understanding of this reaction.1,6-偶极环加成（1,6-Dipolar cycloadditions）是快速构建中环的极具价值的策略。本文报道了一种规避区域选择性的1,6-偶极（1,6-dipoles）设计理念。通过向Morita–Baylis–Hillman（MBH）碳酸酯中引入氨基，本研究以碳酸铯（Cs₂CO₃）为催化剂，精准开发出前所未有的[6+2]偶极环加成反应，可在温和条件下高效合成一系列苯并二氮杂环辛烷（benzodiazocines）。计算研究进一步加深了对该反应的理解。