簡易檢索 / 詳目顯示

回結果列表
研究生： 林寶順
Pao-Shun Lin
論文名稱： 鎳與鈷金屬錯合物催化有機硼試劑與共軛烯類及炔類的加成與環化反應
Nickel and Cobalt-Catalyzed Addition and Cyclization Reactions of Organoboronic Acids with α,β-Unsaturated Alkenes and Alkynes
指導教授： 鄭建鴻
Chien-Hong Cheng
口試委員:
學位類別： 博士
Doctor
系所名稱： 理學院 - 化學系
Department of Chemistry
論文出版年： 2008
畢業學年度： 96
語文別： 英文
論文頁數： 245
中文關鍵詞： 鈷金屬錯合物催化 、有機硼試劑 、共軛烯類 、炔類 、加成反應 、環化反應
外文關鍵詞： Cobalt-Catalyzed, Organoboronic Acids, α,β-Unsaturated Alkenes, Alkynes, Addition Reactions, Cyclization Reactions
相關次數： 點閱：3  下載：0 
分享至:
查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報

    • In this thesis, several new nickel and cobalt catalyzed coupling and cyclization of organoboronic acids with carbon carbon □-components are discussed in detail. For convenience and better clarity, the thesis is divided into five chapters. Chapter 1 describes the over view of synthetic and biological applications of organoboronic reagents. Chapters 2 and 3 demonstrate nickel and cobalt catalyzed Mizoroki Heck and Michael type addition of organoboronic acids to α,β-unsaturated alkenes. The possible reaction mechanisms of Mizoroki Heck and Michael type addition reactions are proposed. A cobalt-catalyzed addition reaction of organoboronic acids with alkynes is described in Chapter 4. Isolation of aryl-cobalt intermediate and correlative cobalt complexes strongly support the proposed mechanism. The annulations of ortho-functionalized arylboronic acids with alkynes for the synthesis of isocoumarin derivatives are presented in Chapter 5 along with the biological applications.

    Acknowledgement iii Abstract vi List of Schemes viii List of Tables xi List of Abbreviations xiii 1 Introduction of Organoboronic Acids and Applications in Metal Catalyzed Reactions 1 1.1 Introduction 2 1.2 Structure and Properties of Boronic Acid Derivatives 3 1.3 The Protocols for Transmetalation of Boronic Acids 4 1.4 Metal Catalyzed Carbon-Carbon Bond Forming Reactions 6 1.4.1 Suzuki Coupling 6 1.4.2 1,4-Additions to Unsaturated Alkenes 8 1.4.3 Addition with Alkenes 12 1.4.4 Addition with Alkynes 18 1.4.5 Tandem Addition Cyclization Reactions 22 1.4.6 1,2-Additions to Carbonyls and Imines 26 1.4.7 Other Intermolecular Cross-Coupling Reactions 28 1.5 Conclusion 28 1.6 References 29 2 Nickel Catalyzed Mizoroki Heck vs. Michael Type Addition of Organoboronic Acids to α,β-Unsaturated Alkenes via Fine Tuning of Ligands 35 2.1 Introduction 36 2.2 Results and Discussion 38 2.2.1 Mizoroki Heck Type Addition Reaction 38 2.2.2 Michael Type Addition Reaction 44 2.3 Mechanistic Considerations 49 2.4 Conclusions 53 2.5 Experimental Section 54 2.6 Spectroscopic Data 56 2.7 References 67 3 Cobalt Catalyzed 1,4 Addition of Organoboronic Acids with α,β-Unsaturated Alkenes 71 3.1 Introduction 72 3.2 Results and Discussion 73 3.3 Mechanistic Considerations 79 3.4 Conclusions 81 3.5 Experimental Section 81 3.6 Spectroscopic Data 81 3.7 References 82 4 Cobalt Catalyzed Regio- and Stereoselective Addition Reaction of Organoboronic Acids with Alkynes 85 4.1 Introduction 86 4.2 Results and Discussion 88 4.3 Mechanistic Considerations 94 4.4 Conclusions 103 4.5 Experimental Section 103 4.6 Spectroscopic Data 106 4.7 References 111 5 Cobalt Catalyzed Highly Regioselective Annulations of ortho-Functionalized Arylboronic Acids with Alkynes for The Synthesis of Isocoumarin Derivatives 115 5.1 Introduction 116 5.2 Results and Discussion 120 5.2.1 The Synthesis of Isochromanone and Isoquinolinone Derivatives 120 5.2.2 The Synthesis of Indenecoumarin Derivatives 128 5.3 Mechanistic Considerations 135 5.4 Conclusions 138 5.5 Experimental Section 138 5.6 Spectroscopic Data 148 5.7 References 158 Appendixes Single Crystal X-ray Data 161 1H and 13C NMR Spectra 185

    [1] a) N. Miyaura, A. Suzuki, J. Chem. Soc. Chem. Commun. 1979, 866; b) N. Miyaura, A. Suzuki, Chem. Rev. 1995, 95, 2457.
    [2] K. Yoshida, T. Hayashi, in Boronic acids: preparation and applications in organic synthesis and medicine, (Ed.: D. G. Hall), Wiley-VCH, Weinheim, 2005.
    [3] a) A. Suzuki, in Metal Catalyzed Cross-Coupling Reactions, (Eds.: F. Diederich, P. J. Stang), Wiley-VCH, Weinheim, 1998. Chapter 2, pp 49; b) Handbook of Organopalladium Chemistry for Organic Synthesis, (Ed.: E. Negishi), John Wiley & Sons, New York, 2002.
    [4] P. B. Tripathy, D. S. Matteson, Synthesis, 1990, 200.
    [5] D. A. Evans, R. P. Polniaszek, K. M. DeVries, D. E. Guinn, D. J. Mathre, J. Am. Chem. Soc. 1991, 113, 7613.
    [6] H. R. Snyder, J. A. Kuck, J. R. Johnson, J. Am. Chem. Soc. 1938, 60, 105.
    [7] D. S. Mattenson, Stereodirected Synthesis with Organoboranes, Springer, Berlin, 1995, pp 1.
    [8] F. Challenger, O. V. Richards, J. Chem. Soc. 1934, 405.
    [9] H. R. Snyder, F. W. Wyman, J. Am. Chem. Soc. 1948, 70, 234.
    [10] H. C. Brown, D. Basavaiah, S. U. Kulkarni, J. Org. Chem. 1982, 47, 3808.
    [11] A. Michaelis, P. Becker, Ber. 1882, 15, 180.
    [12] a) A. Suzuki, H. C. Brown, in Organic Syntheses Via Boranes, Vol 3, Aldrich Chemical Co., Milwaukee, 2003; b) A. Suzuki, J. Organomet. Chem. 1998, 576, 147; mechanism of transmetalation: c) H. Nakai, S. Ogo, Y. Watanabe, Organometallics 2002, 21, 1674; d) M. Retbøll, A. J. Edwards, A. D. Rae, A. C. Willis, M. A. Bennett, E. Wenger, J. Am. Chem. Soc. 2002, 124, 8348; e) K. Matos, J. A. Soderquist, J. Org. Chem. 1998, 63, 461.

    無法下載圖示 全文公開日期 本全文未授權公開 (校內網路)
    全文公開日期 本全文未授權公開 (校外網路)

    QR CODE