Cationic Foldamer‐Catalyzed Asymmetric Synthesis of Inherently Chiral Cages.

Fang, Siqiang; Bao, Zhaowei; Liu, Zanjiao; Wu, Zhengdong; Tan, Jian‐Ping; Wei, Xin; Li, Bo; Wang, Tianli

The stereochemistry of shape‐persistent molecular cages, particularly those resembling prisms, exerts significant influence on their application‐specific functionalities. Although methods exist for fabricating inherently chiral prism‐like cages, strategies for catalytic asymmetric synthesis of these structures in a diversity‐oriented fashion remain unexplored. Herein, we introduce an unprecedented organocatalytic desymmetrization approach for the generation of inherently chiral prism‐like cages via phosphonium‐containing foldamer‐catalyzed SNAr reactions. This methodology establishes a topological connection, enabling the facile assembly of a wide range of versatile stereogenic‐at‐cage building blocks possessing two highly modifiable groups. Furthermore, subsequent stereospecific transformations of the remaining chlorides and/or ethers afford convenient access to numerous functionally relevant chiral‐at‐cage molecules.

ENANTIOSELECTIVE catalysis; STEREOCHEMISTRY; PRISMS; MOLECULES; CHLORIDES; ASYMMETRIC synthesis

Angewandte Chemie, 2024, Vol 136, Issue 46, p1

0044-8249

Academic Journal

10.1002/ange.202411889