Dynamic Kinetic Resolution Polymerization: Synthesis of Chiral Polythioesters from Racemic Monomers

作者：Kun Li, Yue Yang, Min Xie, Qing Cao, Jingliang Cheng, Liang‐Wen Feng, Da‐Gang Yu, Zhongzheng Cai, Jian‐Bo Zhu · 发表于：Angewandte Chemie International Edition · 年份：2025 · DOI：10.1002/anie.202520707 · 被引用次数：6 · 研究领域：Synthesis and Properties of Aromatic Compounds、Axial and Atropisomeric Chirality Synthesis、Carbon dioxide utilization in catalysis

Abstract Chiral polymers are fundamentally important and interesting in nature and scientific research. For the preparation of chiral polymers, the standard kinetic resolution polymerization (KRP) of racemic monomers could only afford a 50% yield of chiral polymers with 50% unreacted monomer leftover. In this contribution, we have developed a dynamic kinetic resolution polymerization (DKRP) strategy to synthesize chiral polymers with complete conversion and improved isoselectivity from racemic monomers. A “Lewis acid/base‐SalBinamAl” catalytic system was employed to achieve efficient DKRP of thiolactones with full monomer conversion and allowed access to chiral polythioesters with perfectly isotacticities ( P m up to 0.99). The formation of chiral polythioesters was confirmed by circular dichroism spectroscopy and optical rotation testing. Detailed kinetic investigation supported a DKRP mechanism. This work represented the very first example of dynamic kinetic resolution ring‐opening polymerization and could provide a new conceptual strategy to guide and inspire the synthesis of chiral polymers from racemic monomers.