Planar chiral [2.2]paracyclophane derivatives are a type of structurally intriguing and practically useful chiral molecules, which have found a range of important applications in the field of asymmetric catalysis and material science. However, access to enantioenriched [2.2]paracyclophanes represents a longstanding challenge in organic synthesis due to their unique structures, which are still highly dependent on the chiral chromatography separation technique and classical chemical resolution strategy to date. In this work, we report on an efficient and versatile kinetic resolution protocol for various substituted amido[2.2]paracyclophanes, including those with pseudo-geminal, pseudo-ortho, pseudo-meta and pseudo-para disubstitutions, using chiral phosphoric acid (CPA)-catalyzed asymmetric amination reaction, which was also applicable to the enantioselective desymmetrization of an achiral diamido[2.2]paracyclophane. Detailed experimental studies shed light on a new reaction mechanism for the electrophilic aromatic C-H amination, which proceeded through sequential triazane formation and N[1,5]-rearrangement. The facile large-scale kinetic resolution reaction and diverse derivatizations of both the recovered chiral starting materials and the C-H amination products showcased the potential of this method.

平面手性[2.2]对环芳烷衍生物是一类结构有趣且实用的手性分子，在不对称催化和材料科学领域具有一系列重要的应用。然而，由于其独特的结构，获得对映体富集的[2.2]对环芳烷是有机合成中长期存在的挑战，迄今为止，这些结构仍然高度依赖于手性色谱分离技术和经典的化学拆分策略。在这项工作中，我们报告了使用手性磷酸（CPA）对各种取代的酰胺基[2.2]对环芳烷进行高效且通用的动力学拆分方案，包括具有假双子、假邻位、假间位和假对位取代的那些。 -催化的不对称胺化反应，也适用于非手性二酰氨基[2.2]对环芳烷的对映选择性去对称化。详细的实验研究揭示了亲电芳香族 CH 胺化的新反应机制，该反应通过连续的三氮烷形成和 N[1,5]-重排进行。回收的手性起始原料和CH胺化产物的简便的大规模动力学拆分反应和多样化的衍生化展示了该方法的潜力。