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The significant scaffold offered by atropisomeric amides with a C–N chiral axis has been extensively utilized for pharmaceuticals, agricultural science, and organic syntheses. As a result, the field of atropisomer synthesis has attracted considerable interest within chemistry communities. To date, a range of catalytic atroposelective approaches has been reported for the efficient construction of these challenging scaffolds. However, greatly concise and highly useful methodologies for the synthesis of these atropisomeric compounds, focusing on transition-metal, chiral amine, and phosphoric acid catalysis reactions, etc., are still desirable. Hence, it is indispensable to succinctly and systematically present all such reports by means of disclosing the mechanistic analysis and application, as well as the challenges and issues associated with the establishment of these atropisomers. In this review, we summarize the development of catalytic asymmetric synthetic strategies to access non-biaryl atropisomers rotating around a C–N chiral axis, including the reaction methods, mechanism, late-stage transformations, and applications.