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.

Department of Chemistry Jadavpur University Kolkata 700032 India

Institute of Organic Chemistry and Biochemistry Czech Academy of Sciences v v i Flemingovo nám 2 Prague 6 16610 Czech Republic

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