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研究生:彭愷恩
研究生(外文):Kai-En Peng
論文名稱:在一級胺化合物上引入氮異環碳烯官能基團之簡易方法
論文名稱(外文):Introduction of NHC Moiety to Primary Amines Through Phthalimide Linkage
指導教授:邱靜雯
指導教授(外文):Ching-Wen Chiu
口試委員:詹益慈李文山
口試委員(外文):Yi-Tsu ChanWen-Shan Li
口試日期:2015-07-01
學位類別:碩士
校院名稱:國立臺灣大學
系所名稱:化學研究所
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2016
畢業學年度:104
語文別:英文
論文頁數:101
中文關鍵詞:氮異環碳烯一級胺化合物
外文關鍵詞:NHCphthalimide linkage
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近年來,氮異環碳烯已被大量地研究,然而氮異環碳烯的合成仍存在一定困難性,特別是高對稱性的橋接型多牙氮異環碳烯,其合成之方式更需改善。為了克服在合成上的困難,我們設計了一個簡易的組裝合成法,將氮異環碳烯單元引入至各式各樣幾何構型的分子骨架中。在此研究中,我們利用一個帶有咪唑鹽與鄰苯二甲酸酐的雙官能型的積木分子,藉由一級胺基與鄰苯二甲酸反應形成的鄰苯二酰亞胺單元將多個氮異環碳烯的前驅物,咪唑鹽,串聯成一維、二維、三維等具有高對稱性骨架之多咪唑鹽化合物,之後在藉由乙基化來合成多牙氮異環碳烯的前驅物。此類氮異環碳烯可進一步與鎳金屬錯合物進行反應,得到各種幾何形狀的多牙氮異環碳烯之鎳金屬錯合物,並應用於末端炔類的氫硫化催化反應。除此之外,我們還將上述之組裝合成方法應用到胺基酸,形成帶有胺基酸分子的咪唑鹽與其相對應的氮異環碳烯前驅物,這些碳烯前去物將來可望合與金屬形成帶有胺基酸分子的有機金屬錯合物,並藉由引入生物分子的方式達到增加氮異環碳烯金屬錯合物的生物活性與選擇性,進一步達到降低投藥量之成效。

N-heterocyclic carbenes (NHCs) have been widely studied recent years. However, the synthesis of NHC could sometimes be complicated, especially when non-chelating symmetrical poly-functional carbene ligands are anticipated. Therefore, we decided to develop a simple method to introduce NHC unit to various molecular backbones using a sole NHC precursor. In this research, a LEGO brick bifunctional ligand, which bears an imidazole moiety on one side of the molecule and phthalic anhydride functionality on the other side, was synthesized. While the imidazole part represents the NHC precursor, the phthalic anhydride group reacts with primary amine containing molecule to introduce the NHC moiety via phthalimide linkage. With this synthetic protocol, poly NHCs and the corresponding poly-nuclear nickel complexes with 1-D, 2-D, and 3-D molecular structure were synthesized. Catalytic performances of these poly-Ni complexes illustrated the negligible interactions between the nickel centers. Furthermore, the synthetic protocol was found to be applicable to various amino acids to give the amino acid tethered benzimidazolium salts and the corresponding metal complexes. The combination of amino acid and NHC ligand is anticipated to improve the bio-compatibility of NHC-metal complexes for selective drug delivery.

CONTENTS
口試委員會審定書
誌謝 i
中文摘要 ii
ABSTRACT iii
CONTENTS iv
LIST OF FIGURES vi
LIST OF SCHEMES vii
LIST OF TABLES viii
Part A Symmetrical Non-Chelating Poly-N-Heterocyclic Carbenes 1
Chapter 1 Introduction 2
1.1 N-Heterocyclic Carbenes 2
1.2 Poly N-Heterocylic Carbenes 5
1.3 Challenges Associated with the Rigid Poly-NHC 6
1.4 Molecular Design 8
Chapter 2 Results and Discussions 10
2.1 Synthesis of the LEGO Brick Molecule 10
2.2 Synthesis of the Poly-amino Compounds 11
2.3 Synthesis of the Poly-Benzimidazoliums via Assembly Method 13
2.3.1 Synthesis of the Bis-benzimidazolium salt 14
2.3.2 Synthesis of the Tris- and Tetrakis-benzimidazolium salts 15
2.4 Syntheses of the Poly N-Heterocyclic Carbene Nickel Complexes 16
2.5 Catalytic Performances of the Poly N-Heterocyclic Carbene Nickel Complexes 20
Chapter 3 Conclusions 22
Chapter 4 Experimental Section 23

Part B Amino Acid-NHC Derivatives and Metal Complexes 37
Chapter 1 Introduction 38
1.1 Bioactive Metal Complexes 38
1.2 Amino Acid Associated Gold Complexes 39
1.3 Obstacles 42
1.4 Synthesis Design 43
Chapter 2 Results and Discussions 44
2.1 Syntheses of the Amino Acid-Tethered Benzimidazoliums 44
2.1.1 Amino Acid-Tethered Benzimidazole 44
2.1.2 Amino Acid-Containing Benzimidazoliums 45
Chapter 3 Conclusions 47
Chapter 4 Experimental Section 48

References 49
Appendix Part A 51
NMR Spectrums 51
Mass Spectrums 66
Appendix Part B 81
NMR Spectrums 81
Mass Spectrums 90


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