[2+2+1]反应合成2,3,5-三取代噻吩衍生物  

The[2+2+1]synthesis of 2,3,5-trisubstituted thiophenes

作　　者：范威 FAN Wei(Office of Research Affairs,Chuzhou City Vocation College,Chuzhou,Anhui,239000 China;College of Chemistry and Chemical Engineering,Nanjing University,Nanjing,Jiangsu,210023 China)

机构地区：[1]滁州城市职业学院科研处,安徽滁州239000 [2]南京大学化学化工学院,江苏南京210023

出　　处：《北京师范大学学报（自然科学版）》2020年第4期542-548,共7页Journal of Beijing Normal University(Natural Science)

基　　金：安徽省教育厅科研重点资助项目(KJ2020A1252);滁州城市职业学院“质粒抽提创新团队”资助项目。

摘　　要：噻吩骨架存在于替诺立定、西他生坦、莫他匹酮等生物碱中,可用作抗炎药、降压药、PDE3抑制剂.对该骨架的修饰,一直是有机合成的热点.在碱促进下,1,4-二羰衍生物和硫氰基芳酮经[2+2+1]反应,构建了噻吩骨架,同时实现了C-2位和C-5位的双芳酰基化、C-3位的芳基化.分别从红外、核磁、质谱和单晶不同角度证实了产物的结构.该反应机制涉及[3+2]环加成、原位开环、互变异构、SN2反应等过程.Thiophene skeleton is present in alkaloids tinoridine,sitaxentan and motapizone,used as antiinflammatory drugs,anti-hypertensive drugs,and PDE3 inhibitors.Modifications of this skeleton are highly desired.Under the promotion of alkali,1,4-dicarbonyls and thiocyanato aryl ketone could undergo[2+2+1]reaction to construct thiophene skeleton.Simultaneously,bisaroylation at C-2 and C-5 positions and arylation at C-3 position were realized.Infrared,nuclear magnetic,mass spectrometry and single crystal all confirmed structure of the product.The reaction should involve[3+2]cycloaddition,in situ ring opening,tautomerization,SN2 reaction and other processes.

关 键 词：[2+2+1]反应 噻吩骨架 双芳酰基化 芳基化 

分 类 号：O626[理学—有机化学]