偕双硅高烯丙胺的硅基aza-Prins环化反应研究  

Study on Silyl-aza-Prins Cyclization of GeminalBis( silyl) Homoallylic Amines

作　　者：唐志星 宋宣毅 周佳静 高璐[1] 宋振雷[1] TANG Zhi-xing;SONG Xuan-yi;ZHOU Jia-jing;GAO Lu;SONG Zhen-lei(West China School of Pharmacy,Sichuan University,Chengdu 610041,China)

机构地区：[1]四川大学华西药学院

出　　处：《合成化学》2019年第8期584-588,599,共6页Chinese Journal of Synthetic Chemistry

基　　金：国家自然科学基金优青项目(21622202)

摘　　要：在三氟甲磺酸三甲基硅酯作用下,偕双硅高烯丙胺与醛发生硅基aza-Prins环化反应,合成了9个C4位含环外烯基硅的新型哌啶类化合物,收率47%~96%,其结构经1H NMR,13C NMR和LC-MS(ESI)表征,Z/E比由产物的1H NMR分析得到;主要异构体的环外烯基硅构型经1H,1H COSY和NOE确证。醛上取代基的电子效应对所生成的烯基硅的构型有较大影响:芳环取代对应Z-式构型,拉电子酯基取代对应单一的E-式构型产物。Geminal bis(silyl)homoallylic amines undergo silyl-aza-Prins cyclization with aldehydes in the presence of TMSOTf at-78℃.The reaction affords nine novel piperidines containing an exocyclic vinylsilane at the C4 position in the yields ranging from 47%to 96%.The structures are characterized by 1 H NMR,13C NMR and LC-MS(ESI),the Z/E ratios are determined by 1 H NMR of the crude products and the configuration of the vinylsilane of the major isomers are assigned by their 1 H,1H-COSY and NOE.The substituents on the aldehydes have great impacts on the configurational outcome of the resulting vinylsilane:aryl substitution provides Z-isomer predominantly,while ester substitution leads to E-isomer completely.

关 键 词：三氟甲磺酸三甲基硅酯 偕双硅高烯丙胺 aza-Prins环化 哌啶环 构型 

分 类 号：O626.32[理学—有机化学] O621.25[理学—化学]