Zhang Qi, Chiou Mong-Feng, Ye Changqing, Yuan Xiaobin, Li Yajun, Bao Hongli
Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, State Key Laboratory of Structural Chemistry, Center for Excellence in Molecular Synthesis, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences 155 Yangqiao Road West Fuzhou Fujian 350002 P. R. China
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences Lingling Road 345 Shanghai 200032 P. R. China.
Chem Sci. 2022 May 2;13(23):6836-6841. doi: 10.1039/d2sc00902a. eCollection 2022 Jun 15.
Herein, we report an intermolecular, radical 1,2,3-tricarbofunctionalization of α-vinyl-β-ketoesters to achieve the goal of building molecular complexity the one-pot multifunctionalization of alkenes. This reaction allows the expansion of the carbon ring by a carbon shift from an all-carbon quaternary center, and enables further C-C bond formation on the tertiary carbon intermediate with the aim of reconstructing a new all-carbon quaternary center. The good functional group compatibility ensures diverse synthetic transformations of this method. Experimental and theoretical studies reveal that the excellent diastereoselectivity should be attributed to the hydrogen bonding between the substrates and solvent.
在此，我们报道了α-乙烯基-β-酮酯的分子间自由基1,2,3-三碳官能化反应，以实现构建分子复杂性的目标——烯烃的一锅多官能化反应。该反应通过全碳季碳中心的碳迁移实现碳环的扩展，并能够在三级碳中间体上进一步形成碳-碳键，目的是重建一个新的全碳季碳中心。良好的官能团兼容性确保了该方法具有多样的合成转化。实验和理论研究表明，优异的非对映选择性应归因于底物与溶剂之间的氢键作用。
