Palladium-Catalyzed C-H Bond Functionalization and Iron-Catalyzed Addition and Annulation Reactions

簡易檢索 / 詳目顯示

回結果列表

研究生：	甘迪潘 GANDEEPAN
論文名稱：	Palladium-Catalyzed C-H Bond Functionalization and Iron-Catalyzed Addition and Annulation Reactions 鈀金屬催化碳—氫鍵活化及鐵金屬催化加成及環化反應之研究
指導教授：	鄭建鴻 Cheng, Chien-Hong
口試委員:	劉瑞雄 Liu, Rai-Shung 蔡易州 Tsai, Yi-Chou 劉緒宗 Liu, Shiuh-Tzung 謝仁傑 Hsieh, Jen-Chieh
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：	2012
畢業學年度：	100
語文別：	英文
論文頁數：	375
中文關鍵詞：	鈀、鐵、碳—氫鍵活化、加成反應、環化反應
外文關鍵詞：	PALLADIUM, IRON, C-H ACTIVATION, ADDITION REACTION, ANNULATION REACTION
相關次數：	點閱：3 下載：0
分享至:	分享至facebook 分享至twitter

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

Transition metal-catalyzed direct transformations of inactivated CH bonds into various functional groups have emerged as a powerful method in organic synthesis. This methodology is fascinating for the chemical and pharmaceutical industries, because it can significantly simplify and shorten the synthetic route and also allow the utilization of less expensive, more readily available, and environmentally benign starting materials. Use of palladium complexes for CH bond functionalization to deduce new synthetic procedures which are more environmentally benign, atom efficient and economically viable than the existing methods was the motivation behind to the current works. With this regards, this thesis describes five new transformations (Chapter 1-5) for CC bond formation through CH bond activation using palladium catalyst.
Iron is 4th most abundant metal on earth and has been increasingly explored in modern catalysis to discover its unique and novel reactivity towards carbon–carbon and carbon–heteroatom bond formation. Owing to its inexpensive and environmentally friendly characteristics, considerable effort has been directed towards iron catalysis and as a result a series of novel iron-catalyzed organic transformations have been developed. Use of such low-cost and non-toxic iron complexes as catalysts in new CC and and Cheteroatom bond formation is highly desirable. With this concern, we also developed three new methods to synthesize -chlorovinyl ketones, ,-alkynyl ketones and 2,4-substituted Quinolines using iron-catalyzed reaction system (Chapter 6-7).

 Chapter 1 decribes the synthesis of phenanthrone derivatives from sec-alkyl aryl ketones with aryl iodides using palladium catalyst. The catalytic reaction appears to proceed via a dual CH activation and enolate cyclization.

 Chapter 2 depicts the synthesis of fluorenones by Pd-catalyzed oxidative cyclization of diaryl ketones. This methodology had advantages using readily available diaryl ketone starting materials to produce variety of fluorenones. This simple method offers an alternative and complimentary way to other fluorenone synthesis.

 Chapter 3 demonstrates an effective palladium-catalyzed carboncarbon double bond assisted selective ortho CH olefination of arenes at room temperature using dioxygen as the oxidant. The reaction appears to be the first example employing an allylic alkenyl double bond as a directing group for CH activation.

 Chapter 4 deals about the synthesis of substituted naphthalenes via palladium catalyzed CH activation and annulation of allyl arenes with alkynes. This reaction proceed through the -coordination of Pd(II) to the allylic carboncarbon double bond and ortho selective CH bond activation. The reaction adds an advantage to use environmentally friendly oxygen as a terminal oxidant.

 Chapter 5 showed an efficient and convenient method for the synthesis of symmetrically substituted 1,4-diaryl-1,3-butadienes by palladium-catalyzed oxidative dimerization of vinyl arenes. The reaction proceeds with broad substrate scope and excellent stereo selectivity.

 Chapter 6 elaborates the development of a very mild and convenient iron-catalyzed addition of acid chlorides to terminal alkynes to give the corresponding -chloroalkenyl ketones in very good yields with excellent regio- and stereoselectivity. The present iron-catalyzed addition reaction is successfully extended to alkynylsilanes to give alkynyl ketones.

 Chapter 7 reveals the synthesis of quinoline derivatives from iron catalyzed tandem reaction of aldimines with styrenes. This process can provide diverse range of quinoline derivatives in good to excellent yields from simple starting materials. The method has advantages of broad substrate scope, simple operation, mild reaction condition, and high effectiveness from non toxic and inexpensive iron catalyst. This reaction also extended to one-pot tandem three-component reaction of aldehydes, styrenes and amines to synthesis of quinoline derivatives.

    Page
ACKNOWLEDGEMENT    v
ABSTRACT    vii
LIST OF SCHEME    x
LIST OF TABLES    xvi
ABBREVIATIONS    xviii
LIST OF PUBLICATIONS    xx

CHAPTER 1 
    Synthesis of Phenanthrone Derivatives from sec-Alkyl Aryl Ketones and Arylhalides via a PalladiumCatalyzed Dual CH Bond Activation and Enolate Cyclization    
1 Introduction    2
1.1 Introduction to CH Functionalization    2
1.2 Introduction to Present Work    4
2 Objective    10
3 Results and Discussion    11
3.1 Optimization of the Reaction    11
3.2 Scope of the Reaction for ortho-Arylation of Aryl Ketones    13
3.3 Synthesis of Phenanthrone Derivatives    15
4 Mechanistic Discussion    18
4.1 Proposed Mechanism    18
4.2 Evidence for the Proposed Mechanism    19
5 Conclusion    21
6 Experimental Section    21
7 Spectroscopic Data    25
8 References    35
    
CHAPTER 2 
    Synthesis of Fluorenones from Diaryl Ketones via PdCatalyzed Oxidative Double CH Bond Activations    
1 Introduction     39
1.1 Oxidative CH Coupling Reaction    39
1.2 Intramolecular Oxidative CH Coupling Reactions    39
1.3 Introduction to Fluorenones    42
1.4 Classical Methods for the Synthesis of Fluorenones    43
1.5 Transition-Metal-Catalyzed Synthesis of Fluorenones    44
2 Objective    47
3 Results and Discussion    48
3.1 Optimization Study for Suitable Solvent    48
3.2 Optimization Study for Suitable Oxidant    49
3.3 Scope of the Reaction    50
4 Mechanistic Discussion    54
5 Conclusion    54
6 Experimental Section    55
7 Spectroscopic Data    55
8 References    61
    
CHAPTER 3 
    Allylic Carbon Carbon Double Bond Directed  PdCatalyzed Oxidative ortho-Olefination of Arenes    
1 Introduction    65
1.1 MizorokiHeck Reaction    66
1.2 FujiwaraMoritani Reaction    67
1.3 Introduction to Present Work    68
2. Objective    76
3 Results and Discussion    76
3.1 Initial Investigations with Styrene    76
3.2 Optimization Studies for the Pd-Catalyzed ortho Alkenation of Allyl Arens    77
3.3 Scope of the Olefins in Pd-Catalyzed Alkenation Reaction    80
3.4 Scope of Allyl Arene Derivatives    83
4 Mechanistic Discussion    86
4.1 Competition study of substituted allyl arenes    86
4.2 Kinetic Isotope Studies    87
4.3 Proposed Mechanism    88
5 Conclusion    89
6 Experimental Section    90
7 Spectroscopic Data    96
8 References    114
    
CHAPTER 4 
    Synthesis of Highly Substituted Naphthalenes via PdCatalyzed ortho-CH Activation and Annulation of Allyl Arenes with Alkynes    
1 Introduction    120
1.1 Introduction to CH Activation and Annulation Reactions    120
1.2 Palladium-Catalyzed to CH Activation and Annulation Reactions    122
1.3 -Chelation-Assisted CH Activation    125
2 Objective    127
3 Results and Discussion    128
3.1 Reaction Optimization    128
3.2 Scope of Naphthalene formation with Symmetrical Alkynes    130
3.3 Scope and Selectivity of Unsymmetrical Alkynes    133
4 Mechanistic Discussion    135
4.1 Proposed Mechanism    135
5 Conclusion    136
6 Experimental Section    136
7 Spectroscopic Data    138
8 References    148
    
CHAPTER 5 
    PalladiumCatalyzed Oxidative Heck-Type Dimerization of Styrenes: An Efficient Method to Synthesis of 1,3Dienes    
1 Introduction    153
1.1 Classical Routes for synthesis of Dienes    153
1.2 Oxidative-Coupling Routes to Synthesis of Dienes    154
1.3 Homodimerization of Vinyl Arenes    156
2 Objective    157
3 Results and Discussion    157
3.1 Reaction Optimization    157
3.2 Scope of the Reaction    159
4 Mechanistic Discussion    163
5 Conclusion    164
6 Experimental Section    165
7 Spectroscopic Data    165
8 References    172
    
CHAPTER 6 
    Iron-Catalyzed Synthesis of -Chlorovinyl and              ,-Alkynyl Ketones from Terminal and Silyl Alkynes with Acid Chlorides    
1 Introduction    177
1.1 Introduction to Addition Reactions    177
1.2 Addition of Acid Chlorides to Alkynes    177
2 Objective    180
3 Results and Discussion    181
3.1 Reaction Optimization for Addition of Acid Chlorides to Alkynes    181
3.2 Scope of FeCl3-Catalyzed Addition of Acid Chlorides to Terminal Alkynes    183
3.3 Scope of Fe-Catalyzed Chloroacylation Reaction to Internal Alkynes    185
3.4 FeCl3-Catalyzed Reaction of Acyl Chlorides with Alkynylsilanes    188
3.5 Scope of FeCl3-Catalyzed ,-Alkynyl Ketones Synthesis    190
4 Mechanistic Discussion    193
4.1 Proposed Mechanism for Addition of Acid Chlorides to Terminal Alkynes    193
4.2 Proposed Mechanism for Addition of Acid Chloride to Internal Alkynes    194
5 Conclusion    196
6 Experimental Section    196
7 Spectroscopic Data    197
8 References    220
    
CHAPTER 7 
    An Easy Access of Quinolines via Fe(III)Catalyzed ThreeComponent Reaction of Aldehydes, Amines and Styrenes    
1 Introduction    225
1.1 Introduction to Quinolines    225
1.2 Synthesis of Quinolines: Traditional Methods    226
1.3 Synthesis of Quinolines: Metal Catalyzed Reactions    227
2 Objective    231
3 Results and Discussion    231
3.1 Reaction Optimization for Quinoline formation    231
3.2 Scope of Quinoline Formation    234
3.3 Fe-Catalyzed Three-Component One-Pot Quinoline Synthesis    237
4 Mechanistic Discussion    238
5 Conclusion    239
6 Experimental Section    239
7 Spectroscopic Data    240
8 References    251
CRYSTAL DATA, 1H AND 13C NMR SPECTRA    254

                                

1. a) Negishi, E.; De Meijere, A. Handbook of Organopalladium Chemistry for Organic Synthesis, Wiley-Interscience, New York, 2002. b) De Meijere A.; Diederich, F. Metal-Catalyzed Cross-Coupling Reactions, Second Completely Revised and Enlarged Edition, Wiley-VCH, 2004. c) Ackermann, L. Modern Arylation Methods, Wiley-VCH, 2009. d) Corbet, J.-P.; Mignani, G. Chem. Rev., 2006, 106, 2651. e) Jana, R.; Pathak T. P.; Sigman, M. S. Chem. Rev., 2011, 111, 1417. f) Muci, A. R.; Buchwald, S. L. Top. Curr. Chem., 2002, 219, 131. g) Hartwig, J. F. Angew. Chem., Int. Ed., 1998, 37, 2046. (h) Rudolph, A.; Lautens, M. Angew. Chem., Int. Ed., 2009, 48, 2656.
2. Godula, K.; Sames. D. Science. 2006, 312, 67.
3. a) Labinger, J. A.; Bercaw, J. E. Nature, 2002, 417, 507. b) Ackermann, L. Chem. Rev., 2011, 111, 1315.
4. a) Trost, B. M. Science, 1991, 254, 1471. b) Trost. B. M. Angew. Chem., Int. Ed., 1995, 34, 259.
5. a) Alberico, D.; Scott, M. E.; Lautens. M. Chem Rev, 2007, 107, 174. b) Lyons, T. W.; Sanford, M. S. Chem. Rev, 2010, 110, 1147.
6. a) Ackermann, L.; Vicente, R.; Kapdi, A. R. Angew. Chem., Int. Ed. 2009, 48, 9792. b) Daugulis, O.; Do, H. Q.; Shabashov, D. Acc. Chem. Res. 2009, 42, 1074.
7. a) Kalyani, D.; Deprez, N. R.; Desai, L. V.; Sanford, M. S. J. Am. Chem. Soc. 2005, 127, 7330. b) Shabashov, D.; Daugulis, O. Org. Lett. 2005, 7, 3657. c) Zaitsev, V. G.; Shabashov, D.; Daugulis, O. J. Am. Chem. Soc. 2005, 127, 13154. d) Ackermann, L. Org. Lett. 2005, 7, 3123. e) Oi, S.; Fukita, S.; Hirata, N.; Watanuki, N.; Miyano, S.; Inoue, Y. Org. Lett. 2001, 3, 2579. f) Ackermann, L.; Althammer, A.; Born, R. Angew. Chem., Int. Ed. 2006, 45, 2619. g) Ackermann, L.; Vicente, R.; Potukuchi, H. K.; Pirovano, V. Org. Lett. 2010, 12, 5032. h) Ackermann, L.; Vicente, R.; Althammer, A. Org. Lett. 2008, 10, 2299. i) Pozgan, F.; Dixneuf, P. H. Adv. Synth. Catal. 2009, 351, 1737. j) Arockiam, P. B.; Fischmeister, C.; Bruneau, C.; Dixneuf, P. H. Angew. Chem., Int. Ed. 2010, 49, 6629.
8. a) Oi, S.; Aizawa, E.; Ogino, Y.; Inoue, Y. J. Org. Chem. 2005, 70, 3113. b) H. –M. Guo, L. –L. Jiang, H. –Y. Niu, W. –H. Rao, L. Liang, R. Z. Mao, D-. Y. Li, G. –R. Qu. Org. Lett. 2011, 13, 2008. c) Ackermann, L.; Vicente, R.; Althammer, A. Org. Lett. 2008, 10, 2299. d) Ackermann, L.; Born, R.; Vicente, R. ChemSusChem 2009, 546. e) Ackermann, L.; Novák, P.; Vicente, R.; Pirovano, V.; Potukuchi, H. K. Synthesis 2010, 2245.
9. a) Daugulis, O.; Zaitsev, V. G. Angew. Chem., Int. Ed. 2005, 44, 4046. b) Lazareva, A.; Daugulis, O. Org. Lett. 2006, 8, 5211.
10. a) Kametani, Y.; Satoh, T.; Miura, M.; Nomura, M. Tetrahedron Lett. 2000, 41, 2655. b) D. Shabasho, O. Daugulis. Org. Lett. 2006, 8, 4947. c) M. Wasa, B. T. Worrell, J. –Q. Yu. Angew. Chem. Int. Ed. 2010, 49, 1275. d) F. Péron, C. Fossey, T. Cailly, F. Fabis. Org. Lett. 2012, 14, 1827.
11. H. A. Chiong, Q. –N. Pham, O. Daugulis. J. Am. Chem. Soc. 2007, 129, 9879.
12. a) Satoh, T.; Kawamura, Y.; Miura, M.; Nomura, M. Angew. Chem., Int. Ed. Engl. 1997, 36, 1740. b) Kawamura, Y.; Satoh, T.; Miura, M.; Nomura, M. Chem. Lett. 1999, 961. c) Kawamura, Y.; Satoh, T.; Miura, M.; Nomura, M. Chem. Lett. 1998, 931. d) Bedford, R. B.; Coles, S. J.; Hursthouse, M. B.; Limmert, M. E. Angew. Chem., Int. Ed. 2003, 42, 112. e) Bedford, R. B.; Limmert, M. E. J. Org. Chem. 2003, 68, 8669. f) Oi, S.; Watanabe, S.-I.; Fukita, S.; Inoue, Y. Tetrahedron Lett. 2003, 44, 8665.
13. a) Terao, Y.; Wakui, H.; Satoh, T.; Miura, M.; Nomura, M. J. Am. Chem. Soc. 2001, 123, 10407. b) Terao, Y.; Wakui, H.; Nomoto, M.; Satoh, T.; Miura, M.; Nomura, M. J. Org. Chem. 2003, 68, 5236. c) Terao, Y.; Nomoto, M.; Satoh, T.; Miura, M.; Nomura, M. J. Org. Chem. 2004, 69, 6942. d) Wakui, H.; Kawasaki, S.; Satoh, T.; Miura, M.; Nomura, M. J. Am. Chem. Soc. 2004, 126, 8658.
14. a) Satoh, T.; Kametani, Y.; Terao, Y.; Miura, M.; Nomura, M. Tetrahedron Lett. 1999, 40, 5345. b) Satoh, T.; Miura, M.; Nomura, M. J. Organomet. Chem. 2002, 653, 151. c) Kakiuchi, F.; Kan, S.; Igi, K.; Chatani, N.; Murai, S. J. Am. Chem. Soc. 2003, 125, 1698. d) Kakiuchi, F.; Matsuura, Y.; Kan, S.; Chatani, N. J. Am. Chem. Soc. 2005, 127, 5936.
15. a) Gürbüz, N.; Özdemir, I.; Çetinkaya, B. Tetrahedron Lett. 2005, 46, 2273. b) Terao, Y.; Kametani, Y.; Wakui, H.; Satoh, T.; Miura, M.; Nomura, M. Tetrahedron 2001, 57, 5967.
16. a) Thirunavukkarasu, V. S.; Parthasarathy, K.; Cheng, C.-H. Angew. Chem., Int. Ed. 2008, 47, 9462. b) Thirunavukkarasu, V. S.; Parthasarathy, K.; Cheng, C.-H. Chem. Eur.J. 2010, 16, 1436.
17. a) Oi, S.; Ogino, Y.; Fukita, S.; Inoue, Y. Org. Lett. 2002, 4, 1783. b) Ackermann, L. Org. Lett. 2005, 7, 3123. c) Ueura, K.; Satoh, T.; Miura, M. Org. Lett. 2005, 7, 2229. d) Desai, L. V.; Hull, L. K.; Sanford, S. M. J. Am. Chem. Soc. 2004, 126, 9542. e) Desai, V.; Malik, H. A.; Sanford, S. M. Org. Lett. 2006, 8, 1141. f) Thu, H.-Y.; Yu, W.-Y.; Che, C.-M. J. Am. Chem. Soc. 2006, 128, 9048. g) Yu, W.-Y.; Sit, W. N.; Lai, K.-M.; Zhou, Z.; Chan, A. S. C. J. Am. Chem. Soc 2008, 130, 3304.
18. a) Chen, X.; Engle, K. M.; Wang, D.-H.; Yu, J.-Q. Angew. Chem., Int. Ed. 2009, 48, 5094. b) Lyons, T. W. Sanford, M. S. Chem. Rev. 2010, 110, 1147. c) Sehnal, P.; Taylor, R. J. K.; Fairlamb, I. J. S. Chem. Rev. 2010, 110, 824.
19. a) Lebrasseur, N.; Larrosa, I.; J. Am. Chem. Soc. 2008, 130, 2926. b) Cho, S. H.; Hwang, S. J.; Chang, S. J. Am. Chem. Soc. 2008, 130, 9254. c) Chen, X.; Googhue, C. E.; Yu, J.-Q. J. Am. Chem. Soc. 2006, 128, 12634. d) Sehnal, P.; Taylor, R. J. K.; Fairlamb, I. J. S. Chem. Rev. 2010, 110, 824.

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)

簡易檢索 / 詳目顯示

相關論文