Li Zhipeng, Zhang Jingyang, Zhu Wanmeng, Wang Tianyi, Tang Yefeng, Wang Jian
School of Pharmaceutical Sciences, Key Laboratory of Bioorganic Phosphorous Chemistry and Chemical Biology, Ministry of Education, Tsinghua University Beijing 100084 China
Chem Sci. 2025 May 5. doi: 10.1039/d5sc01773d.
Heterocalixaromatics play a significant role in supramolecular chemistry and materials science. However, the absence of robust enantioselective synthetic methods has constrained their broader applications. In contrast, the construction of inherently chiral macrocycles -heterocyclic carbene (NHC) remains underexplored to date. We herein report an NHC-catalyzed approach for the rapid assembly of inherently chiral macrocycles. This transformation proceeds a dynamic kinetic resolution (DKR) or kinetic resolution (KR) process, enabling the conversion of racemic substrates into inherently chiral heterocalixaromatics with good to high yields and high to excellent enantioselectivities. DFT calculations were carried out to clarify the chirality control in the related DKR process.
杂杯芳烃在超分子化学和材料科学中发挥着重要作用。然而，缺乏强大的对映选择性合成方法限制了它们的更广泛应用。相比之下，固有手性大环——杂环卡宾（NHC）的构建迄今为止仍未得到充分探索。我们在此报告一种用于快速组装固有手性大环的NHC催化方法。这种转化通过动态动力学拆分（DKR）或动力学拆分（KR）过程进行，能够将外消旋底物转化为固有手性杂杯芳烃，产率良好至高，对映选择性高至优异。进行了密度泛函理论（DFT）计算以阐明相关DKR过程中的手性控制。
