为了合成selaginellin家族天然产物,我们开发了炔锂和对亚甲基苯醌的1,6-加成反应. 研究了此反应的反应条件及底物适用范围和限制. 结果表明,对亚甲基苯醌苯环上的取代基对反应速率和产率有显著的影响:吸电子基团增加其亲电性,使反应变快,并且可以得到较高的产率;与此相反,给电子基团则降低了对亚甲基苯醌的亲电性,反应变慢,并且表现出可逆性,产率变低. 端炔对反应影响很小,均能得到高产率的产物. 本方法可用于快速构建selaginellin家族天然产物的骨架结构.
In order to synthesize selaginellin family natural products, a methodology of 1,6-addition of alkynyl lithium to p-quinone methides was developed.The reaction conditions and scope and limitations of substrates of this reaction were investigated.The results show that the electronic effect of substituents on the phenyl ring of p-quinone methides exhibits significant effects on reaction rates and yields.Electro-withdrawing groups accelerate the addition and lead to good yields.On the other hand, electro-donating groups deactivate p-quinone methides, and low yield is observed presumably due to the equilibrium nature of the reaction.Besides, all alkynes surveyed provide corresponding products in high yield.This novel method can provide a rapid assembly of the skeleton of selaginellin natural products.
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