Wu Yingtao, Guan Xin, Zhao Huaqiu, Li Mingrui, Liang Tianlong, Sun Jiaqiong, Zheng Guangfan, Zhang Qian
Key Laboratory of Functional Organic Molecule Design & Synthesis of Jilin Province, Department of Chemistry, Northeast Normal University Changchun Jilin 130024 China
School of Environment, Northeast Normal University Changchun 130117 China.
Chem Sci. 2024 Feb 24;15(12):4564-4570. doi: 10.1039/d3sc06444a. eCollection 2024 Mar 20.
Axially chiral diaryl ethers bearing two potential axes find unique applications in bioactive molecules and catalysis. However, only very few catalytic methods have been developed to construct structurally diverse diaryl ethers. We herein describe an NHC-catalyzed atroposelective esterification of prochiral dialdehydes, leading to the construction of enantioenriched axially chiral diaryl ethers. Mechanistic studies indicate that the matched kinetic resolutions play an essential role in the challenging chiral induction of flexible dual-axial chirality by removing minor enantiomers over-functionalization. This protocol features mild conditions, excellent enantioselectivity, broad substrate scope, and applicability to late-stage functionalization, and provides a modular platform for the synthesis of axially chiral diaryl ethers and their derivatives.
带有两个潜在轴的轴向手性二芳基醚在生物活性分子和催化领域有着独特的应用。然而，目前仅开发了极少数催化方法来构建结构多样的二芳基醚。我们在此描述了一种由氮杂环卡宾催化的前手性二醛的对映选择性酯化反应，可用于构建对映体富集的轴向手性二芳基醚。机理研究表明，匹配的动力学拆分通过去除次要对映体的过度官能化，在具有挑战性的柔性双轴手性的手性诱导中起着至关重要的作用。该方法具有条件温和、对映选择性优异、底物范围广以及适用于后期官能化等特点，为轴向手性二芳基醚及其衍生物的合成提供了一个模块化平台。
