中文题名: | 手性联芳香Schiff碱配体衍生的钛络合物的合成、结构及其在芳香醛的不对称氢膦化反应中的应用研究 |
姓名: | |
学科代码: | 070303 |
学科专业: | |
学生类型: | 硕士 |
学位: | 理学硕士 |
学位年度: | 2013 |
校区: | |
学院: | |
研究方向: | 金属有机 |
第一导师姓名: | |
第一导师单位: | |
提交日期: | 2013-06-17 |
答辩日期: | 2013-05-07 |
中文摘要: |
本论文以手性(R)-2-氨基-2’-羟基-1,1’-联萘、(R)-2-氨基-2’-羟基-6,6’-二甲基-1,1’-联苯、 (R)-1,1’-联萘-2,2’-二胺和(R)-2,2’-二氨基-6,6’-二甲基-1,1’-联苯为原料合成了8个C1对称性和4个C2对称性的手性配体。这些手性配体可与Ti(OiPr)4反应生成相应的钛络合物。配体的空间位阻在钛络合物的形成过程中起着非常重要的作用。如空间位阻较小的配体13H2与1当量的Ti(OiPr)4反应时得到双配体单核络合物,而空间位阻较大的配体14H2、18H2或21H2与1当量的Ti(OiPr)4反应时却得到单配体单核金属络合物。加热条件下,单配体单核金属络合物可转化为双配体单核金属络合物。例如,在苯溶液中,60 ºC下,单配体单核络合物(14)Ti(OiPr)2 (25)可转化为双配体单核络合物(14)2Ti (26)。全文所得的12个配体和16个钛络合物都通过了各种光谱鉴定和元素分析测试,且所有金属络合物的结构还通过了X-单晶衍射分析。这些手性钛络合物可催化芳香醛的不对称氢膦化反应且显示了较好的催化活性,但立体选择性一般。
﹀
|
外文摘要: |
Eight C1-symmetric and Four C2-symmetric ligands have been designed and successfully prepared from (R)-2-amino-2’-hydroxy-1,1’-binaphthyl, (R)-2-amino-2’-hydroxy-6,6’-dimethyl-1,1’-biphenyl, (R)-2,2’-diamino-1,1’-binaphthyl and (R)-2,2’-diamino-6,6’-dimethyl-1,1’-biphenyl. A series of titanium complexes have been prepared from the reaction between these ligands and Ti(OiPr)4. The steric hindrance of the ligand plays an important role in the titanium complex formation. For example, treatment of ligand 13H2 with 1 equiv of Ti(OiPr)4 gives a chiral bis-ligated titanium complex. While under similar reaction conditions, the more bulky ligands 14H2, 18H2 and 21H2 form the mono-ligated titanium complexes. The mono-ligated titanium alkoxides can be converted to bis-ligated complex via ligand redistribution reaction. For one instance, treatment of mono-ligated complex (14)Ti(OiPr)2 (25) in benzene at 60 ºC results in the isolation of the bis-ligated complex (14)2Ti (26). All the ligands and titanium complexes have been characterized by various spectroscopic techniques and elemental analyses, and all complexes have been further confirmed by X-ray diffraction analyses. The titanium complexes are active catalysts for the asymmetric hydrophosphonylation of aromatic aldehydes, but their enantioselectivities are moderate.
﹀
|
参考文献总数: | 85 |
馆藏号: | 硕070303/1301 |
开放日期: | 2013-06-17 |