Nickel-Catalyzed Cross-Electrophile [2+4] Annulation of Benzynes

Cross-electrophile coupling (XEC) reactions have emerged as a powerful tool for C‒C bond formation, while annulation employ-ing arynes provides unique approaches to polycyclic arenes. Herein, we report a nickel-catalyzed cross-electrophile [2+4] annulation using benzyne and 1-bromo-2-(2-chlorovinyl)arenes as a C-2 and a C-4 synthon, respectively. This proof-of-concept study not only provides a new method to synthesize multi-substituted phenanthrenes but also substantiates the feasibility of merging XEC reaction and aryne chemistry.