Atropisomeric compounds—stereoisomers that arise from the restricted rotation about a single bond—have attracted widespread attention in recent years due to their immense potential for applications in a variety of fields, including medicinal chemistry, catalysis and molecular nanoscience. This increased interest led to the invention of new molecular motors, the incorporation of atropisomers into drug discovery programmes and a wide range of novel atroposelective reactions, including those that simultaneously control multiple stereogenic axes. A diverse set of synthetic methodologies, which can be grouped into desymmetrizations, (dynamic) kinetic resolutions, cross-coupling reactions and de novo ring formations, is available for the catalyst-controlled stereoselective synthesis of various atropisomer classes. In this Review, we generalize the concepts for the catalyst-controlled stereoselective synthesis of atropisomers within these categories with an emphasis on recent advancements and underdeveloped atropisomeric scaffolds beyond stereogenic C(sp²)–C(sp²) axes. We also discuss more complex systems with multiple stereogenic axes or higher-order stereogenicity.

阻转异构体化合物（由单键受限旋转产生的立体异构体）近年来因其在药物化学、催化和分子纳米科学等多个领域的巨大应用潜力而引起了广泛的关注。这种兴趣的增加导致了新分子马达的发明、阻转异构体纳入药物发现计划以及各种新颖的阻转选择性反应，包括同时控制多个立体轴的反应。多种合成方法可分为去对称化、（动态）动力学拆分、交叉偶联反应和从头环形成，可用于催化剂控制的各种阻转异构体类别的立体选择性合成。在这篇综述中，我们概括了这些类别内阻转异构体的催化剂控制立体选择性合成的概念，重点关注了立体异构 C( sp ² )–C( sp ² ) 轴之外的最新进展和尚未开发的阻转异构体支架。我们还讨论了具有多个立构轴或高阶立体异构性的更复杂的系统。