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远程离子基质-催化剂相互作用实现长程立体控制:通过不对称Suzuki-Miyaura 反应获得远程季碳立体中心

Distal Ionic Substrate-Catalyst Interactions Enable Long-Range Stereocontrol: Access to Remote Quaternary Stereocenters through a Desymmetrizing Suzuki-Miyaura Reaction.

机构信息

Department of Chemistry, Faculty of Science, National University of Singapore, 3 Science Drive 3, Singapore 117543.

出版信息

J Am Chem Soc. 2022 Jan 12;144(1):123-129. doi: 10.1021/jacs.1c12345. Epub 2022 Jan 3.

Abstract

Spatial distancing of a substrate's reactive group and nonreactive catalyst-binding group from its pro-stereogenic element presents substantial hurdles in asymmetric catalysis. In this context, we report a desymmetrizing Suzuki-Miyaura reaction that establishes chirality at a remote quaternary carbon. The anionic, chiral catalyst exerts stereocontrol through electrostatic steering of substrates, even as the substrate's reactive group and charged catalyst-binding group become increasingly distanced. This study demonstrates that precise long-range stereocontrol is achievable by engaging ionic substrate-ligand interactions at a distal position.

摘要

在不对称催化中,将底物的反应基团和非反应性催化剂结合基团与其前手性元素隔开会带来很大的障碍。在这种情况下,我们报告了一种去对称的 Suzuki-Miyaura 反应,它在远程季碳上建立了手性。阴离子手性催化剂通过静电引导底物来发挥立体控制作用,即使底物的反应基团和带电荷的催化剂结合基团之间的距离越来越远。这项研究表明,通过在远端位置利用离子的底物-配体相互作用,可以实现精确的远程立体控制。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/995f/9549467/b5afe131205b/ja1c12345_0001.jpg

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