无膦钯催化Heck反应合成新型芳维A酸类化合物  

Phosphine-free Palladium Catalyzed Heck Reaction for the Synthesis of Novel Arotinoic Acids

作　　者：刘西洋[1] 李治章[2] 吴运东[1] 张尊英[1] 梁盛宗[1] 贾晓雷[1] 向建南[1] 

机构地区：[1]湖南大学化学化工学院,长沙410082 [2]湖南科技学院化学系,永州425100

出　　处：《化学学报》2008年第9期1086-1090,共5页Acta Chimica Sinica

基　　金：国家自然科学基金(No.20472018);湖南省自然科学基金(No.07JJY3019);“化学生物传感与计量学”国家重点实验室(No.200607)资助项目

摘　　要：考察了以二环己基胺作配体的无膦钯催化Heck反应条件,建立起一种新型的无膦钯催化Heck反应体系.应用该体系可高收率(72%～84%)、高立体选择性(83%～95%)合成二取代和三取代二苯烯类化合物.以2,4,5-三甲氧基苯乙烯、α-细辛脑为原料,合成了4个尚未见文献报道的新型二苯烯类芳维A酸甲酯(3a,3b,4a,4b),并且在温和的水解体系[LiOH,V(THF)∶V(H2O)=5∶1]下顺利得到了它们的水解产物芳维A酸(5a,5b,6a,6b),产物通过1HNMR,13CNMR,IR和MS进行了结构确认.A phosphine-free palladium-catalyst condition for the Heck reaction using dicyclohexylamine as ancillary ligand was investigated, establishing a new Heck reaction system using phosphine-free palladium-catalyst, which can synthesize di-and tri-substituted stilbene compounds in high yields （72%～84%） and high stereoselectivities （83%～95%）. Four novel stilbene derivatives of arotinoic methyl ester （3a, 3b, 4a and 4b） were synthesized by above method using 2,4,5-trimethoxystyrene and a-asarone as starting materials. Their hydrolysates the arotinoic acids （5a, 5b, 6a and 6b） were easily accessible under mild hydrolysis conditions using the LiOH, THF/H20 （V： V=5 ： 1） system, and all the structures of synthesized compounds were confirmed by ^1H NMR, ^13C NMR, IR and MS techniques.

关 键 词：芳维A酸 苯乙烯衍生物 二苯烯 二环己基胺 钯 HECK反应 LiOH 

分 类 号：O643.32[理学—物理化学]