Laboratoire de Chimie et Biochimie Pharmacolgiques et Toxicologiques - UMR8601 CNRS, Université de Paris, Paris, France.
Chirality. 2021 Sep;33(9):506-527. doi: 10.1002/chir.23335. Epub 2021 Jul 24.
This short review focuses on enantiopure planar chiral [2.2]paracyclophanes (pCps), a fascinating class of molecules that possess an unusual three-dimensional core and intriguing physicochemical properties. In the first part of the review, different synthetic strategies for preparing optically active pCps are described. Although classical resolution methods based on the synthesis and separation of diastereoisomeric products still dominate the field, recent advances involving the kinetic resolution of racemic compounds and the desymmetrization of meso derivatives open up new possibilities to access enantiopure key intermediates on synthetically useful scales. Due to their advantageous properties including high configurational and chemical stability, [2.2]paracyclophanes are increasingly employed in various research fields, ranging from stereoselective synthesis to material sciences. The applications of [2.2]paracyclophanes in asymmetric organocatalysis are described in the second part of the review. While historically enantiopure pCps have been mainly employed by organic chemists as chiral ligands in transition-metal catalysis, these compounds can also be used as efficient catalysts in metal-free reactions and may inspire the development of new transformations in the near future.
这篇简短的综述聚焦于对映纯的平面手性[2.2]对环芳烷（pCps），这是一类具有不寻常的三维核心和有趣物理化学性质的迷人分子。在综述的第一部分，描述了制备光学活性 pCps 的不同合成策略。尽管基于非对映异构体产物的合成和分离的经典拆分方法仍然占据主导地位，但最近涉及外消旋化合物的动力学拆分和内消旋衍生物的去对称化的进展为在合成上有用的规模上获得对映纯关键中间体开辟了新的可能性。由于其有利的性质，包括高构型和化学稳定性，[2.2]对环芳烷在从立体选择性合成到材料科学等各个研究领域中的应用越来越广泛。在综述的第二部分，描述了[2.2]对环芳烷在手性有机催化中的应用。虽然历史上对映纯的 pCps 主要被有机化学家用作过渡金属催化中的手性配体，但这些化合物也可以作为无金属反应中的有效催化剂，并且可能在不久的将来激发新转化的发展。
