Transition-Metal-Catalyzed Nucleophilic Dearomatization of Electron-Deficient Heteroarenes

Abstract In recent decades, transition-metal-catalyzed nucleophilic dearomatization of electron-deficient heteroarenes, such as pyridines, quinolines, isoquinolines and nitroindoles, has become a powerful method for accessing unsaturated heterocycles. This short review summarizes nucleophilic dearomatizations of electron-deficient hetero­arenes with carbon- and heteroatom-based nucleophiles via transition-metal catalysis. A significant number of functionalized heterocycles are obtained via this transformation. Importantly, many of these reactions are carried out in an enantioselective manner by means of asymmetric catalysis, providing a unique method for the construction of enantio­enriched heterocycles. 1 Introduction 2 Transition-Metal-Catalyzed Nucleophilic Dearomatization of Hetero­arenes via Alkynylation 3 Transition-Metal-Catalyzed Nucleophilic Dearomatization of Heteroarenes­ via Arylation 4 Transition-Metal-Catalyzed Nucleophilic Dearomatization of Heteroarenes­ with Other Nucleophiles 5 Transition-Metal-Catalyzed Nucleophilic Dearomatization with Nucleophiles Formed In Situ 6 Conclusion and Outlook