高等学校化学学报

高等学校化学学报 ›› 2003, Vol. 24 ›› Issue (2): 274.

• 论文 • 上一篇    下一篇

新型树状结构手性联二萘酚衍生物的合成及催化性能研究

范青华1, 杨夕强1, 刘国华1, 陈晓闽1, 陈新滋2   

  1. 1. 中国科学院化学研究所分子科学中心, 北京 100080;
    2. 香港理工大学应用生物及化学科技系, 香港
  • 收稿日期:2001-12-03 出版日期:2003-02-24 发布日期:2003-02-24
  • 通讯作者: 范青华(1966年出生),男,博士,副研究员,从事不对称合成研究.E-mail:fanqh@infoc3.icas.ac.cn E-mail:fanqh@infoc3.icas.ac.cn
  • 基金资助:

    国家自然科学基金(批准号:29904009和20132010)资助

Synthesis of New Dendritic Chiral BINOL Ligands and Their Applications in Enantioselective Lewis Acid Catalyzed Addition of Diethylzinc to Aldehydes

FAN Qing-Hua1, YANG Xi-Qiang1, LIU Guo-Hua1, CHEN Xiao-Min1, Albert S. C. Chan2   

  1. 1. Center for Molecular Science, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, China;
    2. Open Laboratory of Chirotechnology and Department of Applied Biology and Chemical Technology, Hong Kong, China
  • Received:2001-12-03 Online:2003-02-24 Published:2003-02-24

PDF (PC)

被引次数

7

摘要： 报道了树状结构的手性联二萘酚(BINOL)配体的合成及其在二乙基锌对醛的不对称加成反应中的应用.(R)-2,2′-二羟基-1,1′-联萘-3,3′-二羧酸与末端为氨基的Frechet聚芳醚型树状分子经缩合反应,以中等产率得到0～3代的树状分子配体,用1HNMR,IR和MALDI-TOF质谱进行了结构表征.这些树状手性配体与Ti(OPri)4在无水甲苯溶液中形成的配合物是二乙基锌对醛不对称加成反应的高效催化剂,树状分子载体的体积对催化剂的对映选择性没有明显的影响.以邻氯苯甲醛为底物时,反应的对映选择性随树状分子代数的增加而有所提高.

关键词: 1, 1-联萘-2-酚, 树状手性大分子, 不对称催化

Abstract: The series of new dendritic chiral BINOL ligands(3) were synthesized by condensation reaction of (R)-2,2′-dihydroxy-1,1′-binaphthyl-3,3′-dicarboxylic acid(1) and Fréchet-type poly(aryl ether) dendrons(2) with an amino group at the focal point in moderate reaction yields. All ligands were characterized by 1HNMR, IR and MALDI-TOF-MS spectra, which clearly demonstrated the formation of monodispersed dendritic BINOLs. The titanium complexes of these dendritic ligands obtained by mixing(3) with Ti(OPri)4 4 in dry toluene were found to be efficient catalysts in asymmetric addition of diethylzinc to aldehydes. The size of the dendritic wedges did not significantly influence the enantioselectivity of the catalyst. Most interestingly, when ortho-chlorobenzaldehyde was used as substrate, we found that enantioselectivity increased slightly with increasing generation of the dendrimers.

Key words: 1,1′-BINOL, Chiral dendrimer, Asymmetric catalysis

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