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研究生:倪英馬
研究生(外文):Nirma Afrisanti Kinasih
論文名稱:胺鍵結氮異環碳烯與雙亞胺吡啶之合成及其應用於無過渡金屬催化之偶合反應
論文名稱(外文):The Synthesis of Amino-Linked Nitrogen-Heterocyclic Carbene and Bis Imino Pyridine and Their Implication in Metal-Free Cross Coupling
指導教授:何郡軒王朝諺
指導教授(外文):Jinn-Hsuan HoTiow Gan Ong
口試委員:何郡軒王朝諺
口試日期:2012-07-11
學位類別:碩士
校院名稱:國立臺灣科技大學
系所名稱:化學工程系
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2012
畢業學年度:100
語文別:英文
論文頁數:178
中文關鍵詞:卡賓氮氨基聯雜環卡賓雙亞胺吡啶金屬無交叉耦合
外文關鍵詞:carbeneamino-linked Nitrogen Heterocyclic carbeneBis Imino PyridineMetal-Free Cross coupling
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N-雜環卡賓(NHC)σ-捐贈作為強大的中性配廣泛用作輔助配體在協助調解催化過渡金屬。我們成功地採用了氨基聯NHC的(1-TBU)調解與各種芳基碘苯和吡啶,不涉及過渡金屬的交叉耦合。我們還發現了另一個系統,使用雙亞胺吡啶配體調解之間的苯和各種芳基碘芳基。已配體的特點是多核(1H,13C)核磁共振光譜,其中一些已經由單晶X-射線衍射特徵。交叉偶聯反應產生的化合物也已被鑑定多核核磁共振,核磁共振光譜和質譜測量。
此外,我們還調查1 TBU系統的動力學同位素效應和激進的途徑。我們發現,金屬碳 - 碳耦合通過單電子轉移機制與自由基中間體多方面參與。我們的發現表明,1 TBU和雙亞胺吡啶配體有前途的交叉耦合,而不訴諸使用過渡金屬調解活動。
N-Heterocyclic Carbene (NHC) as strong neutral σ-donating ligands are widely utilized as auxiliary ligands in assisting transition metal for mediating catalysis. We successfully employed Amino-Linked NHC (1-tBu) to mediate cross coupling of benzene and pyridine with various aryl iodide without involving transition metal. We also found another system using Bis Imino Pyridine as a ligand to mediate arylation between benzene and various aryl iodide. The ligands have been characterized by multinuclear (1H,13C) NMR spectroscopy and some of them have been characterized by single-crystal X-ray diffraction. All of compounds produced from cross coupling reaction also have been characterized by multinuclear 1H NMR, 13C NMR spectroscopy and MS measurements.
In addition, we also investigate kinetic isotope effect and radical pathway in 1-tBu system. We found that the metal-free carbon-carbon coupling manifold via single electron transfer mechanism with radical intermediates involved. Our finding has demonstrated that 1-tBu and Bis Imino Pyridine as a ligand have promising activity for mediating cross coupling without resorting to use transition metal.
Acknowladgement
Abstract
Chapter 1 Introduction
1.1 Carbene
1.2 Nitrogen-Heterocyclic Carbene (NHCs)
1.3 The NHC’s Application in Organometallic Chemistry and Catalysis
1.4 Metal-Free Catalyst System in Organocatalyst for Arylation Reaction
Chapter 2 Result and Discussion
2.1 Synthesis and Characterization of Amino-Linked Carbene
2.2 Synthesis and Characterization of Bis Imino Pyridine
2.3 Amino-Linked Carbene Catalyzed Arylation of Benzene
2.4 Bis Imino Pyridine Catalyzed Arylation of Benzene
Chapter 3 Experimental
3.1 General Procedure....
3.2 Material and Methods
3.3 General Procedure for Cross-Coupling of Aryl Iodides with Benzene
3.4 General Procedure for Cross-coupling of Aryl Iodides with Pyridine
3.5 General Procedure for Arylation of Benzene with Aryl Iodide in the Presence of Bis Imino Pyridine
3.6 The synthesis of Ligand
3.7 Study Kinetic Isotope Effect
3.8 Competition Reaction Between Benzene and Pyridine
Chapter 4 Conclusion
Chapter 5 Reference
Appendix A : Single Crystal X-ray Characterization
Appendix B : 1H and 13C NMR Spectra
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