Zhang Jiwu, Wu Meng, Zhang Zhihan, Chong Qinglei, Meng Fanke
State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Shanghai, China.
College of Chemistry, Central China Normal University, Wuhan, Hubei, China.
Nat Commun. 2025 Jul 1;16(1):5995. doi: 10.1038/s41467-025-61019-2.
Development of catalytic enantioselective transformations through divergent pathways from a single set of starting materials provides one of the most straightforward and efficient strategies for rapid establishment of a library of molecules in chemical synthesis and drug discovery. Catalytic reactions that generate enantioenriched cyclobutenes and cyclobutanes which are not only important units in medicinal chemistry, natural products and material science, but also useful intermediates in organic synthesis are of importance in the field of catalysis. Here we report a cobalt-catalyzed protocol for pathway-divergent enantioselective coupling of alkynes and cyclobutenes. Such processes that begin with oxidative cyclization followed by protonation or reductive elimination accurately controlled by ligands produce densely functionalized cyclobutanes and cyclobutenes in up to 95% yield with >98:2 regio- and diastereoselectivity and >99.5:0.5 enantiomeric ratio. Mechanistic studies and DFT calculations reveal that the reaction pathways are manipulated precisely by ligands and elucidate the origin of stereoselectivity.
通过单一组起始原料的不同途径开发催化对映选择性转化，为在化学合成和药物发现中快速建立分子库提供了最直接有效的策略之一。生成对映体富集的环丁烯和环丁烷的催化反应不仅是药物化学、天然产物和材料科学中的重要单元，也是有机合成中的有用中间体，在催化领域具有重要意义。在此，我们报道了一种钴催化的炔烃与环丁烯的途径发散对映选择性偶联方法。此类过程始于氧化环化，随后进行质子化或还原消除，由配体精确控制，可产生官能团密集的环丁烷和环丁烯，产率高达95%，区域和非对映选择性>98:2，对映体比例>99.5:0.5。机理研究和密度泛函理论计算表明，反应途径由配体精确控制，并阐明了立体选择性的起源。
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