Han Tian-Jiao, Guan Chun-Yan, Li Na, Dong Rui, Xu Li-Ping, Xiao Xiao, Wang Min-Can, Mei Guang-Jian
College of Chemistry, Pingyuan Laboratory, Zhengzhou University, Zhengzhou 450001, China.
School of Chemistry and Chemical Engineering, Shandong University of Technology, Zibo 255000, Shandong, China.
iScience. 2023 Sep 20;26(10):107978. doi: 10.1016/j.isci.2023.107978. eCollection 2023 Oct 20.
Reported herein is a highly efficient dynamic kinetic resolution protocol for the atroposelective synthesis of heterobiaryls with vicinal C-C and N-N diaxes. Atropisomers bearing vicinal diaxes mainly exist in -triaryls, while that of biaryls is highly challenging in terms of the concerted rotation and deplanarization effects. The combination of C-C biaryl with N-N nonbiaryl delivers a novel class of vicinal-diaxis heterobiaryls. For their atroposelective synthesis, the dynamic kinetic resolution enabled by either quinine-catalyzed allylation or isothiourea-catalyzed acylation has been developed, allowing the preparation of a wide range of vicinal-axis heterobiaryls in good yields with excellent enantioselectivities. Atropisomerization experiments revealed that the C-C bond rotation led to diastereomers, and the N-N bond rotation offered enantiomers. Besides, this protocol could be extended to kinetic resolution by employing substrates with a more hindered axis.
本文报道了一种高效的动态动力学拆分方法，用于对映选择性合成具有邻位C-C和N-N二轴的杂联芳基。带有邻位二轴的阻转异构体主要存在于三芳基中，而对于联芳基而言，由于协同旋转和去平面化效应，其合成极具挑战性。C-C联芳基与N-N非联芳基的组合产生了一类新型的邻位二轴杂联芳基。对于它们的对映选择性合成，已经开发了由奎宁催化的烯丙基化或异硫脲催化的酰化实现的动态动力学拆分，从而能够以良好的产率和优异的对映选择性制备多种邻位轴杂联芳基。阻转异构化实验表明，C-C键的旋转导致非对映异构体，而N-N键的旋转产生对映异构体。此外，通过使用具有更受阻轴的底物，该方法可以扩展到动力学拆分。
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