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

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

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(OiPr)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.

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, l＇-binaphthol and 1,4-diazidobenzen in the presence of Copper（ I ）. The composi- tion, structure and morphology of Polymer were characterized by Fourier transform infrared （FTIR） spectrome- ter, powder X-ray diffractometer（XRD） and scanning electron microscope （SEM）. The Polymer was coordina- ted to titanium of Ti （OiPr） 4 through chiral dihydroxy groups in （R） - （＋） -BINOL to synthesize a new heteroge- neous chiral metal catalyst（ Polymer-Ti）, which exhibited extremely high conversion and good enantioselectivi- ty in asymmetric addition reaction of diethylzinc to multiple aromatic aldehydes. Also, Polymer-Ti catalyst dis- played stable catalytic activities in multi-recycle of asymmetric addition reaction of diethylzinc to benzalde- hyde.