SIOC English
化学学报
高级检索

化学学报 ›› 2008, Vol. 66 ›› Issue (9): 1086-1090. 上一篇    下一篇

研究论文

无膦钯催化Heck反应合成新型芳维A酸类化合物

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*,1,3   

  1. (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)
    (3湖南大学生物医学工程中心 长沙 410082)
  • 投稿日期:2007-10-10 修回日期:2007-12-10 发布日期:2008-05-14
  • 通讯作者: 向建南

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

LIU Xi-Yang1 LI Zhi-Zhang2 WU Yun-Dong1 ZHANG Zun-Ying1 LIANG Sheng-Zong1 JIA Xiao-Lei1 XIANG Jian-Nan*13   

  1. (1 College of Chemical and Chemistry Engineering, Hunan University, Changsha 410082)
    (2 Department of Chemistry, Hunan University of Science and Engineering, Yongzhou 425100)
    (3 Biomedical Engineering Center, Hunan University, Changsha 410082)
  • Received:2007-10-10 Revised:2007-12-10 Published:2008-05-14
  • Contact: XIANG Jian-Nan

PDF

655

被引次数

33

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1H NMR, 13C NMR, IR和MS进行了结构确认.

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

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 α-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/H2O (V∶V＝5∶1) system, and all the structures of synthesized compounds were confirmed by 1H NMR, 13C NMR, IR and MS techniques.

Key words: arotinoic acid, styrene derivative, stilbene, dicyclohexylamine, palladium, Heck reaction, LiOH