Nickel‐Catalyzed Efficient, Regioselective One‐Pot Synthesis of 1‐Methyleneindenes via Tandem C–C Bond Formation: Computational Mechanistic Insights and Docking Studies

Abstract Herein, we report a nickel‐catalyzed tandem cyclization–coupling method for the regioselective synthesis of 1‐methyleneindenes and benzofulvenes from 1‐(2,2‐dibromovinyl)‐2‐alkynylbenzenes and aryl boronic acids. The transformation proceeds in the presence of a suitable ligand and base, enabling sequential activation of the C─Br bonds and intra‐molecular alkyne moiety under relatively mild reaction conditions with yields 72%–85%. This robust protocol offers wide range of functional group tolerance in substrate and boronic acid part. Density functional theory (DFT) calculations, in addition, provide thorough mechanistic insights that point to a tandem process of oxidative addition, migratory insertion, and reductive elimination, with key energetic preferences explaining the observed product selectivity.