Lan Shouang, Cui Qinqin, Luo Defu, Shi Siyu, He Chengyang, Huang Shengyu, Xu Chao, Zhao Lili, Liu Jinggong, Gu Cheng-Zhi, Yang Shuang, Fang Xinqiang
State Key Laboratory of Structural Chemistry, Center for Excellence in Molecular Synthesis, Fujian Institute of Research on the Structure of Matter, University of Chinese Academy of Sciences, Fuzhou 350100, China.
School of Chemistry and Chemical Engineering, Shihezi University, Shihezi 832000, China.
J Am Chem Soc. 2025 Jan 8;147(1):1172-1185. doi: 10.1021/jacs.4c14944. Epub 2024 Dec 26.
Catalytic asymmetric transformation of donor-acceptor cyclopropanes (DACs) has been proven to be a highly valuable and robust strategy to construct diverse types of enantioenriched molecules. However, the use of 1,1,2,2-tetrasubstituted DACs to form products bearing quaternary stereocenters remains a long-term unsolved challenge. Here, we report the copper-catalyzed asymmetric aminative ring opening of tetrasubstituted alkynyl DACs that delivers a myriad of α-tertiary amines with high levels of enantioselectivities. The alkyne, amine, and ester moieties within the products enable diverse further applications, including the asymmetric synthesis of bioactive molecules. Mechanistic studies indicate that the zwitterionic intermediate bearing a copper-acetylide unit plays a key role in the process, which represents a new mode for achieving catalytic asymmetric transformation of DACs.
供体-受体环丙烷（DACs）的催化不对称转化已被证明是构建各种对映体富集分子的一种非常有价值且稳健的策略。然而，使用1,1,2,2-四取代的DACs来形成带有季碳立体中心的产物仍然是一个长期未解决的挑战。在此，我们报道了铜催化的四取代炔基DACs的不对称胺化开环反应，该反应能以高对映选择性提供多种α-叔胺。产物中的炔基、胺基和酯基可实现多种进一步的应用，包括生物活性分子的不对称合成。机理研究表明，带有铜-乙炔化物单元的两性离子中间体在该过程中起关键作用，这代表了实现DACs催化不对称转化的一种新模式。
