利用薯蓣皂甙元完整骨架合成新的.docVIP

氨卤加成反应在天然产物结构改造中的应用 陈战国，魏俊发※,周利燕,王 芸,赵朋飞,石先莹 陕西师范大学化学与材料科学学院 陕西 西安 710062 E-mail: weijf@snnu.edu.cn 本文报道一种非常方便的利用薯蓣皂甙元完整骨架合成新的含氮丙啶侧环的甾体皂甙元新方法。利用氨卤加成反应策略，以对甲苯磺酰胺和N-溴代丁二酰亚胺作为氮源和卤素源，铝粉作催化剂，在薯蓣皂甙元的5,6位双健上分别引入溴和磺酰氨基。在室温下，用无水K2CO3作催化剂，以小分子酰胺作为助催化剂定量的合成出含有氮丙啶侧环的甾体皂甙元(收率100 %)。目标化合物结构经 1H NMR、13C NMR和元素分析确证。 参考文献： [1] Xu,Q.W.; Peng, X. W.; Tian,W. S. Tetrahedron Letters, 2003, 44, 9375. [2] 唐小枚许启海田伟生化学学报, 2007, 65(20)2315. [3] 田伟生许启海陈玲中国科学 B辑 化学, 2004, 34(1)33. [4] 林静容王玉春田伟生化学学报, 2007, 65(16) 1685. [5] Thakur, V.V.; Talluri, S.K.; Sudalai, A. Organic letters. 2003, 5(6), 861. [6] Li, G.; S. R. S. Saibabu Kotti, Timmons, C. Eur. J. Org. Chem. 2007, 2745. [7] Wang, Y.N.; Adiseshu, K.; Teng, A. Tetrahedron Letter. 2007, 48, 7894. 关键词：氨卤加成反应，天然产物，结构改造，应用 Application of Aminohalogenation for Structure Reformation of nature product Chen Zhan-Guo, Wei Jun-Fa(, Zhou Li-Yan, Wang Yun, Zhao Peng-Fei, Shi Xian-Ying School of Chemistry and Materials Science, Shaanxi Normal University, Xi’an, 710062 A steriod sapogenin derivative containing p-toluenesulfonamido aziridine side cycle has been synthesized by using the intact skeleton of diosgenin with a convenient approach. The bromine and p-toluenesulfonamido groups were simultaneous introduced on the carbon-carbon double bonds of 5,6-positions in the diosgenin skeleton catalyzed by aluminum powder in dichloromethane at room temperature with TsNH2/NBS as nitrogen and bromine sources, respectively. The intramolecular nucleophilic substitution reaction in diosgenin skeleton was carried out smoothly catalyzed by a poor base in acetone affording nearly quantitative yield of target compound at room temperature. The structure of target compound was confirmed by 1H NMR, 13C NMR and elemental analysis.