Synthesis of N–N Atropisomers via De Novo Construction of Nitrogen‐Containing Heterocycles

In recent years, the N–N atropisomers have drawn increasing attention compared to their well‐developed C–C and C–N analogs due to their potential application in biological and material chemistry. Since the first report in 2021, catalytic asymmetric synthesis of N–N atropisomers has become an emerging research topic, and strategies, including asymmetric N−H bond functionalization, asymmetric desymmetrization, and atroposelective de novo construction of heterocycles, are developed to offer this novel atropisomeric framework. In this review, we summarize the recent advancements in catalytic asymmetric synthesis of N–N atropisomers via de novo construction of nitrogen‐containing heterocycles, such as pyrroles, indoles, isoquinolones, benzimidazoles, isoindolinones, quinazolinones, dihydropyridinones, and pyrimidinones.