方酰胺催化的环状磺酰亚胺不对称胺化反应  

Asymmetric Amination of Cyclic N-sulfonylimines Catalyzed by Squaric Amide

作　　者：周全[1] 董琳[1] 

机构地区：[1]四川大学华西药学院,四川成都610041

出　　处：《合成化学》2013年第4期381-386,共6页Chinese Journal of Synthetic Chemistry

基　　金：国家自然科学基金资助项目(21202106)

摘　　要：首次报道了方酰胺催化环状磺酰亚胺α-位的不对称胺化反应。以N-环状磺酰亚胺与偶氮二羧酸酯为原料,在方酰胺催化下经Michael加成反应构建C-N键,合成了一系列新型糖精衍生物;1-(1,1-二氧代苯并异噻唑-3-基)-1-肼二甲酸二苄酯丁烷经还原、关环反应得含尿素结构的并环衍生物,其结构经1H NMR,13C NMR和HR-MS表征。并考察了反应温度、反应时间和底物结构对胺化反应的影响。结果表明,以奎宁方酸胺为催化剂时,最佳反应条件为:二氯甲烷为溶剂,4MS为添加剂,于-30℃反应24 h,收率95%～99%,84%e.e.～94%e.e.。A series of novel saccharin derivatives were synthesized by asymmetric α-amination of cyclic N-sulfonylimines with hydrogen bonding catalyst in moderate conditions.A polycyclic product was obtanied by reduction and cyclization reaction of dibenzyl 1-[1-（1,1-dioxidobenzo[d]isothiazol-3-yl）butyl]hydrazine-1,2-dicarboxylate.The structures were characterized by 1H NMR,13C NMR,and HR-MS.The effect of temperature,reaction time and the structure of the substrate on asymmetric α-amination were investigated.The results showed that the optimum reaction conditions at-30 ℃ for 24 h were as follows： dichloromethane was the solvent,4 MS was the catalyst promoter,the yield was 95%～99% with 84%e.e.～94%e.e..

关 键 词：方酰胺 不对称胺化反应 环状磺酰亚胺 α-位胺化 催化剂 合成 

分 类 号：O623.732[理学—有机化学] O625.1[理学—化学]