Recent Progress of Electron‐Withdrawing‐Group‐Tethered Arenes Involved Asymmetric Nucleophilic Aromatic Functionalizations

Abstract Electron‐withdrawing groups (EWG) have emerged as a powerful tool for the activation of various arenes to promote nucleophilic dearomative additions for the construction of complicated chiral cyclic structures under asymmetric catalytic systems. Nitro‐indoles, nitro‐benzofurans/benzothiophenes, and related nitro‐heteroarenes are widely applied in the reaction with various nucleophiles to construct various enantioenriched polycyclic skeletons via the asymmetric dearomatization process. Meanwhile, the electron‐deficient azo‐group and nitroso‐group are an alternative powerful tool for the activation of arenes, which enable formal nucleophilic aromatic arylations with various electrophilic aromatics to construct novel chiral biaryl atropisomers. Besides, azo‐naphthanenes are served as dipolar surrogates in the reaction with nucleophilic dipolarophiles to proceed asymmetric cycloadditions to construct chiral polycyclic skeletons. The EWG‐tethered arene has proven to be a versatile protocol for the construction of structurally diversified chiral backbones. This review summarizes the latest progress of the EWG‐tethered arenes involved asymmetric transformations under organo‐ or transition metal catalysis. magnified image