CC Coupling Reactions of Superstrong CF3 Groups with C(sp2)–H Bonds: Reactivity and Synthetic Utility of Zero‐Valent Niobium Catalyst

It was found that zero-valent niobium is an efficient catalyst for the intramolecular C-C coupling reactions of o-aryl and o-alkenyl alpha,alpha,alpha-trifluorotoluene derivatives. The superstrong C-F bonds of CF3 groups and neighboring C(sp2)-H bonds were doubly activated, and fluorenes and indenes were obtained in good yields. The niobium fluorocarbenoid species is proposed to be the key intermediate.