Asymmetric synthesis of mechanically planar chiral rotaxanes and topologically chiral catenanes has been a long-standing challenge in organic synthesis. Recently, an excellent strategy was developed based on diastereomeric synthesis of rotaxanes and catenanes with mechanical chirality followed by removal of the chiral auxiliary. On the other hand, its enantioselective approach has been quite limited. Here, we report enantioselective preparation of mechanically planar chiral rotaxanes by kinetic resolution of the racemates via remote asymmetric acylation of a hydroxy group in the axis component, which provides an unreacted enantiomer in up to >99.9% ee in 29% yield (the theoretical maximum yield of kinetic resolution of racemate is 50%). While the rotaxane molecules are expected to have conformational complexity, our original catalysts enabled to discriminate the mechanical chirality of the rotaxanes efficiently with the selectivity factors in up to 16.

机械平面手性轮烷和拓扑手性链烷的不对称合成一直是有机合成中的长期挑战。近来，基于具有机械手性的轮烷和链烷的非对映体合成，然后除去手性助剂，开发了一种优异的策略。另一方面，其对映选择性的方法是非常有限的。在这里，我们报告了通过轴组分中羟基的远程不对称酰化，通过外消旋物的动力学拆分，通过机械拆分外消旋物的对映体，制备了对映体，该对映体的未反应对映体的ee值高达99.9％，产率为29％（理论上的最大值）外消旋物的动力学拆分产率为50％。预计轮烷分子具有构象复杂性，