Leibniz-Institute for Catalysis, Albert-Einstein-Straße 29a, 18059, Rostock, Germany.
Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Key Laboratory of Organosilicon Material Technology of Zhejiang Province, Hangzhou Normal University, No. 2318, Yuhangtang Road, 311121, Hangzhou, P. R. China.
Angew Chem Int Ed Engl. 2020 Nov 23;59(48):21585-21590. doi: 10.1002/anie.202006550. Epub 2020 Sep 17.
The first general and regioselective Pd-catalyzed cyclocarbonylation to give α-methylene-β-lactones is reported. Key to the success for this process is the use of a specific sterically demanding phosphine ligand based on N-arylated imidazole (L11) in the presence of Pd(MeCN) Cl as pre-catalyst. A variety of easily available alkynols provide under additive-free conditions the corresponding α-methylene-β-lactones in moderate to good yields with excellent regio- and diastereoselectivity. The applicability of this novel methodology is showcased by the direct carbonylation of biologically active molecules including natural products.
首次报道了钯催化的普遍的、区域选择性的环羰化反应，生成α-亚甲基-β-内酰胺。该反应成功的关键是在 Pd(MeCN)Cl 预催化剂的存在下，使用基于 N-芳基咪唑的特定空间位阻膦配体（L11）。各种易得的炔醇在无添加剂条件下，以中等至良好的收率，极好的区域和非对映选择性，得到相应的α-亚甲基-β-内酰胺。该新方法的适用性通过包括天然产物在内的生物活性分子的直接羰基化反应得到了展示。
