高等学校化学学报 ›› 2013, Vol. 34 ›› Issue (5): 1052-1058.doi: 10.7503/cjcu20121011

• 研究论文: 无机化学 • 上一篇    下一篇

利用"Click"反应制备含有(R)-(+)-BINOL的有机聚合物及其钛配合物在不对称加成反应中的催化性能

刘健, 石鑫   

  1. 辽宁师范大学化学化工学院功能材料化学研究所, 大连 116029
  • 收稿日期:2012-11-07 出版日期:2013-05-10 发布日期:2013-05-10
  • 通讯作者: 石 鑫, 女, 博士, 副教授, 主要从事有机-无机杂化材料的合成及应用研究. E-mail: xinshi@lnnu.edu.cn E-mail:xinshi@lnnu.edu.cn
  • 基金资助:

    国家自然科学基金(批准号: 21173108)和国家"九七三"计划项目(批准号: 2009CB220010)资助.

Preparation of Organic Polymer Containing (R)-(+)-BINOL Through "Click" Reaction and Catalytic Performance of Its Ti Complex in Asymmetric Addition Reaction

LIU Jian, SHI Xin   

  1. Institute of Chemistry for Functionalized Materials, School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, China
  • Received:2012-11-07 Online:2013-05-10 Published:2013-05-10

摘要:

以自制的(R)-(+)-1,1'-联二萘酚[(R)-(+)-BINOL]的衍生物(R)-(+)-6,6'-二乙炔-1,1'-联二萘酚和1,4-对苯二叠氮为原料, 经由"Click"反应(Huisgen 1,3-偶极环加成反应)制备出含有(R)-(+)-BINOL的有机聚合物(Polymer), 利用傅里叶变换红外光谱仪(FTIR)、 粉末X射线衍射仪(XRD)和扫描电子显微镜(SEM)对Polymer的组成、 结构和形貌进行了表征. Polymer经过与Ti(OemPr)4配位合成出一种新型的非均相手性金属催化剂(Polymer-Ti), 该催化剂在催化二乙基锌和多种芳香醛的不对称加成反应中都表现出非常高的芳香醛转化率和较好的对映体选择性, 而且可以在二乙基锌和苯甲醛的不对称加成反应中循环使用.

关键词: 非均相手性金属催化剂, "Click"反应, 不对称催化

Abstract:

An organic polymer containing chiral (R)-(+)-1,1'-binaphthol [(R)-(+)-BINOL] building blocks(Polymer) has been prepared through "Click" reaction(Huisgen 1,3-dipolar cycloaddition) of (R)-(+)-6,6'-diethynyl-1,1'-binaphthol and 1,4-diazidobenzen in the presence of Copper(Ⅰ). The composition, structure and morphology of Polymer were characterized by Fourier transform infrared(FTIR) spectrometer, powder X-ray diffractometer(XRD) and scanning electron microscope(SEM). The Polymer was coordinated to titanium of Ti(OemPr)4 through chiral dihydroxy groups in(R)-(+)-BINOL to synthesize a new heterogeneous chiral metal catalyst(Polymer-Ti), which exhibited extremely high conversion and good enantioselectivity in asymmetric addition reaction of diethylzinc to multiple aromatic aldehydes. Also, Polymer-Ti catalyst displayed stable catalytic activities in multi-recycle of asymmetric addition reaction of diethylzinc to benzaldehyde.

Key words: Heterogeneous chiral metal catalyst, "Click", reaction, Asymmetric catalysis

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