新型NNO三齿手性联萘酚配体的合成及其催化二乙基锌与芳醛加成反应及其镍配合物的合成

论文摘要

最近几年,许多科学家对合成NNO手性配体及它们的配合物用于各种各样的有机反应产生了极大兴趣。联萘酚是一种广泛用于合成手性配体的非常有效的手性inductor。对于联萘酚及其衍生物的研究的兴趣来源于它们具有手性、C2对称性、灵活性、易于合成等特征。该论文的主要工作有以下几个方面：我们报道了了两个基于联萘酚骨架的NNO三齿手性配体。这两个化合物都是由3,3`-二醛基联萘酚与两个具有N,N-二配位原子的胺缩合而合成出来的。这两个化合物的合成分离的产率非常高。我们对这两个化合物进行了1HNMR,13CNMR, FTIR, MALDI-TOF等测试。我们还合成了它们镍的配合物并对配合物进行了表征。配合物的晶体结构表明它们是双核或三核体系。另外,我们还尝试了它们用于不同催化反应的催化性能。我们尝试将3,3`-二喹啉取代的手性配体用于二乙基锌与醛的不对称加成反应。实验结果表明3,3``-二喹啉取代的化合物在二乙基锌的作用下能够催化该反应而生成二级醇。我们设计并合成了NNN-三齿胺-亚胺配体,并且合成了它的单配体锌的配合物。我们对配体及配合物进行了详细的表征。单配体锌的配合物晶体结构表明该结构为单配体结构,锌中心原子为四配位的。3,3`-二喹啉取代的手性配体被用作接受器而用于金属阳离子的检测。实验结果表明该接收器能够选择性识别锌离子。

论文目录

• Preface
• 提要
• 摘要
• Abstract
• CHAPTER Ⅰ
• 1.1 Introduction
• 1.2 BINOL and Derivatives
• 1.2.1 Introduction
• 1.2.2 BINOL Chirality
• 1.2.3 BINOL Chirality Based on Atropisomerism
• 1.2.4 C2-Symmetry and Binapthols
• 1.3 Properties and Synthesis of BINOL
• 1.3.1 Introduction
• 1.3.2 Preparation of （R）-BINOL and （S）-BINOL
• 1.4 Chirality
• 1.4.1 Origin and Importance of Chirality
• 1.4.2 Consequences of Chirality
• 1.4.3 Routes to Synthesize Enantiopure Compounds
• 1.5 Schiff base ligands
• 1.5.1 Synthesis of Schiff base ligands
• 1.5.2 Synthesis of chiral binapthyl Schiff base ligands
• 1.5.3 Schiff base transition metal complexes
• 1.5.4 Applications of Schiff base transition metal complexes
• 1.6 Scope of the present thesis
• Chapter Ⅱ Synthesis and Characterization of chiral BINOL ligandsbearing NNO donors, their Nickel Complexes and ligands applications inpolymerization reaction
• 2.1 Introduction
• 2.2 Nickel
• 2.2.1 Introduction to Norbornene Polymerization
• 2.2.2 Introduction to ring opening polymerization
• 2.3 Experimental Sections
• 2.3.1 General Considerations
• 2.3.2 Measurements
• 2.3.3 Synthesis
• 2.4. Synthesis of chiral BINOL Schiff-base ligands
• 2.4.1 Synthesis and characterization of （R）-5a
• 2.4.2 Synthesis and characterization of （R）-5b
• 2.5 Synthesis and characterization of metal complexes
• 2.5.1 Synthesis of Complex 2a
• 2.5.2 Synthesis of Complex 2b
• 2.5.3 Ring opening Polymerimerization of complex 2a
• 2.5.4 Polymerization of norbornene
• 2.6 Results and Discussions
• 2.7 Characterizations of the different compounds
• 2.8 Conclusion
• CHAPTER Ⅲ Enantioselective Addition of Diethylzinc to ArylAldehydes Catalyzed by 3,3'-bis （quinolin-8-ylimino） methyl)-1,1'-binaphthyl-2,2'-diol
• 3.1 Introduction
• 3.2 Critical factors and current problems for the application of homogeneous catalysts
• 3.3 Experimental Section
• 3.3.1 General procedure
• 3.3.2 Spectroscopic and analytical data
• 3.4 Results and Discussions
• 3.5 Conclusion
• CHAPTER Ⅳ Synthesis, Characterization of Ligand and Complex ofethyl-zinc complex bearing a tridentate NNN anilinido-aldimine ligand
• 4.1 Introduction
• 4.2 Experimental Section
• 4.2.1 General Method
• 4.2.2 Synthesis of the ligand
• 4.3 Characaterization of the ligand and the complex
• 4.4 Application in Ring-Opening Polymerization of lactide
• 4.5 Results and Discussions
• 4.6 Conclusion
• 2+ based onChiral BINOL Schiff base ligand 3,3'-bis（quinolin-8-ylimino）methyl)-1,1'-binaphthyl-2,2'-diol'>Appendix #153CHAPTER Ⅴ Selective Fluorescent Chemosensor for Zn²⁺ based onChiral BINOL Schiff base ligand 3,3'-bis（quinolin-8-ylimino）methyl)-1,1'-binaphthyl-2,2'-diol
• 5.1 Introduction
• 5.2 Fluorescent molecular sensors of ions and molecules
• 5.2.1 Fundamental aspects
• 5.2.2 Different terms used for fluorescents sensors
• 5.2.3. Molecular Sensors
• 5.2.4 Aim and objective of this part
• 5.3 Experimental Section
• 5.3.1 Materials
• 5.3.2 Characterization and techniques
• 5.3.3 Binding studies
• 5.4 Results and Discussion
• 5.5 Conclusion
• References
• Acknowledgements
• Publications
• Abbreviations and Symbols