Zhuang Qing-Bo, Tian Jin-Rui, Lu Ka, Zhang Xiao-Ming, Zhang Fu-Min, Tu Yong-Qiang, Fan Rong, Li Zhi-Hao, Zhang Yu-Dong
State Key Laboratory of Applied Organic Chemistry & College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, China.
School of Chemistry and Chemical Engineering, Frontier Scientific Center of Transformative Molecules, Shanghai Key Laboratory of Chiral Drugs and Engineering, Shanghai Jiao Tong University, Shanghai Minhang 200240, China.
J Am Chem Soc. 2023 Dec 13;145(49):26550-26556. doi: 10.1021/jacs.3c11178. Epub 2023 Nov 29.
A catalytic enantioselective polycyclization of tertiary enamides with terminal silyl enol ethers has been developed by virtue of Cu(OTf) catalysis with a novel spiropyrroline-derived oxazole (SPDO) ligand. This tandem reaction offers an effective approach to assemble bicyclic and tricyclic -heterocycles bearing both - and -quaternary stereogenic centers, which are primal subunits in a range of natural alkaloids. Strategic application of this methodology and a late-stage radical cyclization as key steps have been showcased in the concise total synthesis of (-)-cephalocyclidin A.
借助铜（三氟甲磺酸盐）催化和一种新型螺吡咯啉衍生的恶唑（SPDO）配体，已开发出一种叔烯酰胺与末端硅基烯醇醚的催化对映选择性多环化反应。这种串联反应为组装含有α-和β-季碳立体中心的双环和三环杂环提供了一种有效方法，这些杂环是一系列天然生物碱的主要亚基。在（-）-头环环定A的简洁全合成中展示了该方法的策略性应用以及后期自由基环化作为关键步骤。
