Construction of CF₃‑Functionalized Fully Substituted Benzonitriles through Rauhut–Currier Reaction Initiated [3 + 3] Benzannulation

Though numerous cyanation reactions have been developed for the synthesis of benzonitriles, the construction of valuable fully substituted benzonitriles is still a challenging task. Herein, we reported a tertiary amine-catalyzed [3 + 3]-benzannulation for the green synthesis of CF3-functionalized fully substituted benzonitriles. This strategy features exclusive chemoselectivity, high atom-economy, and good step-economy with environment-friendly reagents and mild conditions. Unique triphenyl-substituted dicyanobenzoate products could be rapidly constructed using this method. The practicality and reliability of this reaction were proved by the successful scale-up synthesis. A mechanistic study indicates that the [3 + 3]-benzannulation was initiated by an intermolecular Rauhut–Currier reaction.