Escape from Palladium: Nickel-Catalyzed Catellani Annulation

J Am Chem Soc. 2023 May 24;145(20):11005-11011. doi: 10.1021/jacs.3c03780. Epub 2023 May 15.

Abstract

While Catellani reactions have become increasingly important for arene functionalizations, they have been solely catalyzed by palladium. Here we report the first nickel-catalyzed Catellani-type annulation of aryl triflates and chlorides to form various benzocyclobutene-fused norbornanes in high efficiency. Mechanistic studies reveal a surprising outer-sphere concerted metalation/deprotonation pathway during the formation of the nickelacycle, as well as the essential roles of the base and the triflate anion. The reaction shows a broad functional group tolerance and enhanced regioselectivity compared to the corresponding palladium catalysis.