Enantioselective Synthesis of Inherently Chiral Calix[4]arenes via Palladium-Catalyzed Asymmetric Intramolecular C–H Arylations

作者：Yuzhen Zhang, Mengmeng Xu, Xu‐Ge Si, Jun‐Li Hou, Quan Cai · 发表于：Journal of the American Chemical Society · 年份：2022 · DOI：10.1021/jacs.2c10606 · 被引用次数：89 · 研究领域：Axial and Atropisomeric Chirality Synthesis、Metal-Organic Frameworks: Synthesis and Applications、Synthesis and Properties of Aromatic Compounds

We report herein an efficient approach for the enantioselective synthesis of inherently chiral calix[4]arenes via palladium-catalyzed asymmetric intramolecular C–H arylations. Using a chiral bifunctional phosphine-carboxylate ligand, the inherent chirality on macrocyclic scaffolds was induced successfully, from which a wide range of calix[4]arenes with fluorenone motifs were obtained with good yields and excellent enantioselectivities (up to >99% ee). The synthetic utility of this method was demonstrated by diverse transformations of the products, thus substantially expanding the chemical space of chiral calix[4]arenes. Further investigations of photophysical and chiroptical properties revealed that calix[4]arenes bearing two fluorenone moieties displayed remarkable g lum values (up to 0.019), highlighting the great potential of inherent chirality in the development of organic optoelectronic materials.