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研究生： 卡迪克
Karthikeyan
論文名稱： Cobalt-, Palladium- and Rhodium-Catalyzed C–C Bond Formations via Addition and C–H Functionalization Reactions
鈷、鈀及銠金屬催化碳—碳鍵生成反應：碳—氫鍵官能基化及加成反應之研究
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
謝仁傑
Hsieh, Jen-Chieh
劉緒宗
Liu, Shiuh-Tzung
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： 305
中文關鍵詞： Cobalt 、Palladium 、Rhodium 、Asymmetric Addition reactions 、C-H bond activations
外文關鍵詞： Cobalt, Palladium, Rhodium, Asymmetric Addition reactions, C-H bond activations
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    • Transition-metal-catalyzed C‒C bond formation reaction by uniting readily available π-components is an attractive strategy to synthesis biologically important compounds in a single operation with high atom-efficacy. Particularly, asymmetric synthesis and C H bond activation reactions are competent method to synthesis biologically important compounds in a highly regio- and stereoselective manner. In this regard, this thesis describes ten new reactions that focus on the asymmetric addition of arylboronic acids with aldehydes, bicyclic alkenes, which were successfully achieved by tuning different kinds of chiral ligands in the presence of air stable cobalt catalyst system. The C H functionalization of arylboronic acids with heteroarenes and N-methoxybenzamides to afford various functionalized biaryls. On the other hand multiple C H activations of
    N-methoxybenzamides with simple arenes and alkenes afforded biologically active phenanthridinone and isoindolinone derivatives in one-pot manner. For better understanding, I divided this thesis into seven chapters. The first three chapters describe about cobalt-catalyzed addition reactions of aldehydes and bicyclic alkenes with organoboronic acids. The fourth chapter describe about cobalt-catalyzed direct arylation reaction of heteroarenes with organoboronic acids. The next two chapters deal with palladium-catalyzed C-H activation reactions of N-methoxybenzamides with simple arenes and alkenes. The final chapter describe about the dual C H activations of
    N-methoxybenzamides with arylboronic acids using rhodium(III) as the catalyst.

    TABLE OF CONTENTS Page ABSTRACT IV LIST OF SCHEMES VI LIST OF TABLES VIII ABBREVIATIONS X LIST OF PUBLICATIONS XIII CHAPTER 1: Cobalt-Catalyzed Addition Reaction of Organoboronic Acids with Aldehydes: Highly Enantioselective Synthesis of Diarylmethanols 1 1.1 General Introduction 2 1.2 Introduction to present work 5 1.3 Results and Discussion 8 1.4 Proposed Stereochemical Model 18 1.5 Conclusion 18 1.6 Experimental Section 18 1.7 Spectroscopic Data 23 1.8 HPLC Data 31 1.9 References 34 CHAPTER 2: Synthesis of Biarylketones and 3-Substituted Phthalides from Organoboronic acids and Aldehydes Catalyzed by Cobalt Complexes 37 2.1 Introduction 38 2.2 Results and Discussion 43 2.3 Proposed Mechanism for Cobalt-Catalyzed Addition Reaction of Aldehydes with Arylboronic acids 49 2.4 Conclusion 53 2.5 Experimental Section 54 2.6 Spectroscopic Data 55 2.7 References 67 CHAPTER 3: Cobalt-Catalyzed Stereoselective Ring-Opening of Oxa, Aza- and Diaza Bicyclic Alkenes with Arylboronic Acids: Synthesis of 1,2-Dihydro-1-Naphthol, 1-Naphthylamine and 3,4-disubstituted hydrazino cyclopentene Derivatives 70 3.1 Introduction 71 3.2 Results and Discussion 77 3.3 Proposed Mechanism for cobalt-catalyzed ring-opening reaction of bicyclic alkenes with arylboronic acids 86 3.4 Proposed Mechanism for Ring opening Reaction of diazabicycle with Organoboronic Acids. 90 3.5 Conclusion 91 3.6 Experimental Section 91 3.7 Spectroscopic Data 94 3.8 HPLC Data 107 3.9 References 108 CHAPTER 4: Cobalt Catalyzed Direct C H Arylation of Azoles with Aryl Boronic acids 111 4.1 Introduction 112 4.2 Results and Discussion 115 4.3 Proposed Mechanism 120 4.4 Conclusion 120 4.5 Experimental Section 121 4.6 Spectroscopic Data 121 4.7 References 126 CHAPTER 5: Synthesis of Phenanthridinones from N-Methoxybenzamides and Arenes by Multiple Palladium-Catalyzed C-H Activation Steps at Room Temperature 129 5.1 Introduction 130 5.2 Results and Discussion 136 5.3 Mechanistic Discussion 143 5.4 Conclusion 144 5.5 Experimental Section 145 5.6 Spectroscopic Data 146 5.7 References 154 CHAPTER 6: Palladium Catalyzed Heterocyclization of N-Methoxy Benzamides with Alkenes under Room Temperature 157 6.1 Introduction 158 6.2 Results and Discussion 164 6.3 Mechanistic Discussion 171 6.4 Conclusion 172 6.5 Experimental Section 173 6.6 Spectroscopic Data 173 6.7 References 182 CHAPTER 7: Rh(III)-Catalyzed Oxidative C H Coupling of N-Methoxybenzamides with Arylboronic acids: One-pot Synthesis of Phenanthridinones under Mild Conditions 184 7.1 Introduction 185 7.2 Results and Discussion 190 7.3 Mechanistic Discussion 196 7.4 Conclusion 197 7.5 Experimental Section 197 7.6 Spectroscopic Data 198 7.7 References 208 CRYSTAL STRUCTURES, 1H AND 13C NMR spectra 212

    1. (a) Schmidt, F.; Stemmler, R. T.; Rudolph, J.; Bolm, C. Chem. Rev. 2006, 35, 454. (b) Fagnou, K.; Lautens, M. Chem. Rev. 2003, 103, 169. (c) Bolm, C.; Hildebrand, J. P.; Muniz, K.; Hermanns, N. Angew. Chem., Int. Ed. 2001, 40, 3284. (d) Darses, S.; Genet, J. P. Eur. J. Org. Chem. 2003, 4313.
    2. (a) Furstner, A. Chem. Rev. 1999, 99, 991. (b) Guijarro, D.; Yus, M. Tetrahedron 2000, 56, 1135. (c) Boymond, L.; Rottlander, M.; Cahiez, G.; Knochel, P. Angew. Chem., Int. Ed. 1998, 37, 1701. (d) Lee, J. S.; Velarde, O. R.; Guijarro, A.; Wurst, J. R.; Rieke, R. D. J. Org. Chem. 2000, 65, 5428. (e) Weber, B.; Seebach, D. Tetrahedron 1994, 50, 7473. (f) Noyori, R.; Kitamura, M. Angew. Chem., Int. Ed. 1991, 30, 49. (g) Oi, S.; Moro, M.; Inoue, Y.; Organometallics 2001, 20, 1036. (h) Fujii, T.; Koike, T.; Mori, A.; Osakada, K. Synlett 2002, 298. (i) Ogawa, Y.; Mori, M.; Saiga, A.; Takagi, K. Chem. Lett. 1996, 1069. (j) Kondo, Y.; Takazawa, N.; Yamazaki, C.; Sakamoto, T. J. Org. Chem. 1994, 59, 4717.
    3. Some selected reviews and book: (a) Yoshida, K.; Hayashi, T. in Boronic acids: preparation and applications in organic synthesis and medicine, (Ed.: D. G. Hall), Wiley-VCH, Weinheim, 2005. (b) Suzuki, A. Acc. Chem. Res. 1982, 15, 178. (c) Kudo, N.; Perseghini, M.; Fu, G. C. Angew. Chem. 2006, 118, 1304; Angew. Chem. Int. Ed. 2006, 45, 1282. (d) Kotha, S.; Lahiri, K.; Kashinath, D. Tetrahedron 2002, 58, 9633. for potassium organotrifluoroborates see (e) Darses, S.; Genet, J.-P. Chem. Rev. 2008, 108, 288. (f) Molander, G. A.; Ellis, N. Acc. Chem. Res, 2007, 40, 275. (g) Navarre, L.; Darses, S.; Genet, J.-P. Angew. Chem, 2004, 116, 737; Angew. Chem. Int. Ed. 2004, 43, 719. (h) Darses, S.; Genet, J.-P. Eur. J. Org. Chem. 2003, 4313. (j) Pucheault, M.; Darses, S.; Genet, J.-P. Chem. Commun. 2005, 4714.
    4. Sakai, M.; Ueda, M.; Miyaura, N. Angew. Chem. Int. Ed. 1998, 37, 3279.
    5. Some selected papers for Rh: (a) Focken, T.; Rudolph, J.; Balm, C. Synthesis 2005, 429. (b) Ueda, M.; Miyaura, N. J. Org. Chem. 2000, 65, 4450. (c) Huang, R.; Shaughnessy, K. H. Chem. Commun. 2005, 4484. (d) Batey, R. A.; Thadani, A. N.; Smil, D. V. Org. Lett. 1999, 1, 1683. (e) Hayashi, T. Takahashi, M.; Takaya, Y.; Ogasawara, M. J. Am. Chem. Soc. 2002, 124, 5052. (f) Gois, P. M. P.; Trindade, A. F.; Veiros, L. F.; Andre, V.; Duarte, M. T.; Afonso, C. A. M.; Caddick, S.; Cloke, F. G. N. Angew. Chem Int. Ed. 2007, 46, 5750. (g) Krause, H.; Furstner, A. Adv. Synt. Cat. 2001, 343.
    6. Yamamoto, T.; Ohta, T.; Ito, Y. Org. Lett. 2005, 7, 4153.
    7. Kuriyama, M.; Shimazawa, R.; Shirai, R. J. Org. Chem. 2008, 73, 1597.
    8. Liao, Y.-X.; Xing, C.-H.; He, P. Hu, Q.-S. Org. Lett., 2008, 10, 2509.
    9. (a) Takahashi, G.; Shirakawa, E.; Tsuchimoto, T.; Kawakami, Y. Chem. Commun. 2005, 1459. (b) Arao, T.; Kondo, K.; Aoyama, T. Tetrahedron Lett. 2007, 48, 4115.
    10. For Cu: Zheng, H.; Zhang, Q.; Chen, J.; Liu, M.; Cheng, S.; Ding, J.; Wu, H.; Su, W. J. Org. Chem. 2009, 74, 943. For Fe: Zou, T.; Pi, S.-S.; Li, J.-H. Org. Lett. 2009, 11, 453.
    11. Lin, P.-S.; Jeganmohan, M.; Cheng, C.-H. Chem. Eur. J. 2008, 14, 11296.
    12. (a) Meguro, K.; Aizawa, M.; Sohda, T.; Kawamatsu, Y.; Nagaoka, A. Chem. Pharm. Bull. 1985, 33, 3787. (b) Corey, E. J.; Helal, C. J. Tetrahedron Lett. 1996, 37, 5675. (c) Botta, M.; Summa, V.; Corelli, F.; DiPietro, G.; Lombardi, P. Tetrahedron: Asymmetry 1996, 7, 1263. (d) Stanchev, S.; Rakovska, R.; Berova, N.; Snatzke, G.; Tetrahedron: Asymmetry 1995, 6, 183. (e) Bolshan, Y.; Chen, C.; Chilenski, J. R.; Gosselin, F.; Mathre, D. J.; O'Shea, P. D.; Roy, A.; Tillyer, R. D. Org. Lett. 2004, 6, 111. (f) Toda, F.; Tanaka, K.; Koshiro, K. Tetrahedron: Asymmetry 1991, 2, 873. (g) Barouh, V.; Dall, H.; Patel, D.; Hite, G. J. Med. Chem. 1971, 14, 834.
    13. (a) Corey, E. J.; Helal, C. J. Angew. Chem. 1998, 110, 2092; Angew. Chem. Int. Ed. 1998, 37, 1986. (b) Corey, E. J.; Bakshi, R. K.; Shibata, S. J. Am. Chem. Soc. 1987, 109, 5551.
    14. (a) Ohkuma, T.; Koizumi, M.; Ikehira, H.; Yokozawa, T.; Noyori, R. Org. Lett. 2000, 2, 659. (b) Noyori, R.; Ohkuma, T. Pure Appl. Chem. 1999, 71, 1493.
    15. Bolm, C.; Rudolph, J.; J. Am. Chem. Soc. 2002, 124, 14850.
    16. Duan, H.-F.; Xie, J.-H.; Shi, W.-J.; Zhang, Q.; Zhou, Q.-L. Org. Lett. 2006, 8, 1479.
    17. Yamamoto, Y.; Kurihara, K.; Miyaura, N. Angew. Chem. Int. Ed. 2009, 48, 4414.
    18. Liao, Y.-X.; Xing, C.-H.; Hu, Q.-S. Org. Lett., 2012, 14, 1544.
    19. Wei, C.-H.; Mannathan, S.; Cheng, C.-H. J. Am. Chem. Soc. 2011, 133, 6942.
    20. (a) Lin, P.-S.; Jeganmohan, M.; Cheng, C.-H. Chem. Asian J. 2007, 2, 1409. (b) Chang, H.-T.; Jayanth, T. T.; Wang, C.-C.; Cheng, C.-H. J. Am. Chem. Soc. 2007, 129, 12032. (c) Chang, H.-T.; Jayanth, T. T.; Cheng, C.-H. J. Am. Chem. Soc. 2007, 129, 4166. (d) Wang, C.-C.; Lin, P.-S.; Cheng, C.-H. J. Am. Chem. Soc. 2002, 124, 9696. (e) Wang, C.-C.; Lin, P.-S.; Cheng, C.-H. Tetrahedron Lett. 2004, 45, 6203. (f) Wong, Y.-C.; Parthasarathy, K.; Cheng, C.-H. J. Am. Chem. Soc. 2009, 131, 18252. (g) Mannathan, S.; Cheng, C.-H. Chem. Commun. 2010, 46, 1923. (h) Karthikeyan, J.; Parthasarathy, K.; Cheng, C.-H. Chem. Commun. 2011, 47, 1046.42, 31
    1) (a) Surburg, H.; Panten, J. Common Fragrance and Flavor Materials, 5th ed.; Wiley-VCH: Weinheim, Germany, 2006. (b) Deng, Y.; Chin, Y.-W.; Chai, H.; Keller, W. J.; Kinghorn, A. D. J. Nat. Prod. 2007, 70, 2049. (c) Romins, K. R.; Freeman, G. A.; Schaller, L. T.; Cowan, J. R.; Gonzales, S. S.; Tidwell, J. H.; Andrews, C. W.; Stammers, D. K.; Hazen, R. J.; Ferris, R. G.; Short, S. A.; Chan, J. H.; Boone, L. R. J. Med. Chem. 2006, 49, 727. (d) Masson, P. J.; Coup, D.; Millet, J.; Brown, N. L. J. Biol. Chem. 1994, 270, 2662.
    2) (a) Furstner, A.; Voigtlander, D.; Schrader, W.; Giebel, D.; Reetz, M. T. Org. Lett. 2001, 3, 417. (b) Song, C. E.; Shim, W. H.; Roh, E. J.; Choi, J. H. Chem. Commun. 2000, 1695. (c) Ross, J.; Xiao, J. Green Chem. 2002, 4, 129. (d) Gmouh, S.; Yang, H.; Vaultier, M. Org. Lett. 2003, 5, 2219. (e) Nara, S. J.; Harjani, J. R.; Salunkhe, M. M. J. Org. Chem. 2001, 66, 8616. (f) Fillion, E.; Fishlock, D.; Wilsily, A.; Goll, J. M. J. Org. Chem. 2005, 70, 1316. (g) Furstner, A.; Voigtlander, D.; Schrader, W.; Giebel, D.; Reetz, M. T. Org. Lett. 2001, 3, 417.
    3) (a) Posner, G. H.; Whitten, C. E.; McFarland, P. E. J. Am. Chem. Soc. 1972, 94, 5106. (b) Karpov, A. S.; Muller, T. J. Org. Lett. 2003, 5, 3451. (c) Kim, S.-H.; Rieke, R. D. J. Org. Chem. 2000, 65, 2322. (d) Lee, P. H.; Lee, S. W.; Seomoon, D. Org. Lett. 2003, 5, 4963. (e) Larock, R. C.; Lu, Y. J. Org. Chem. 1993, 58, 2846. (f) Hart, D. W.; Schwartz, J. J. Am. Chem. Soc. 1974, 96, 8115. (g) Hegedus, L. S.; Kendall, R. M.; Lo, S. M.; Sheats, J. R. J. Am. Chem. Soc. 1975, 97, 5448. (h) Duplais, C.; Bures, F.; Sapountzis, I.; Korn, T. J.; Cahiez, G.; Knochel, P. Angew. Chem. Int. Ed. 2004, 43, 2968.
    4) (a) Hirao, T.; Misu, D.; Agawa, T. J. Am. Chem. Soc. 1985, 107, 7179. (b) Byrne, B.; Karras, M. Tetrahedron Lett. 1987, 28, 769. (c) Pelter, A.; Smith, K. Tetrahedron Lett. 1989, 30, 5643.
    5) (a) Jun, C.-H.; Lee, H.; Hong, J.-B. J. Org. Chem. 1997, 62, 1200. (b) Jun, C.-H.; Lee, D.-Y.; Lee, H.; Hong, J.-B. Angew. Chem. Int. Ed. 2000, 39, 3070.
    6) Ishiyama, T.; Hartwig, J. F. J. Am. Chem. Soc. 2000, 122, 12043.
    7) (a) Huang, Y.-C.; Majumdar, K. K.; Cheng, C.-H. J. Org. Chem. 2002, 67, 1682. (b) Shukla, P.; Cheng. C.-H. Org. Lett. 2006, 8, 2867.
    8) Ko, S.; Kang, B.; Chang, S. Angew. Chem. Int. Ed. 2005, 44, 455.
    9) Ishiyama, T.; Kizaki, H.; Hayashi, T.; Suzuki, A.; Miyaura, N. J. Org. Chem. 1998, 63, 4726.
    10) (a) Bumagin, N. A.; Korolev, D. N. Tetrahedron Lett. 1999, 40, 3057. (b) Haddach, M.; McCrathy, J. R. Tetrahedron Lett. 1999, 40, 3109.
    11) Liebeskind, L. S.; Srogl, J. Am. Chem. Soc. 2000, 122, 11260.
    12) (a) Goossen, L. J.; Ghosh, K. Angew. Chem. Int. Ed. 2001, 40, 3458. (b) Goossen, L. J.; Ghosh, K. Eur. J. Org. Chem. 2002, 3254. (c) Goossen, L. J.; Ghosh, K. Chem. Commun. 2001, 2084. (d) Frost, C. G.; Wadsworth, K. J. Chem. Commun. 2001, 2316.
    13) Wong, Y.-C.; Parthasarathy, K.; Cheng, C.-H. Org. Lett. 2010, 12, 1736.
    14) (a) Pucheault, M.; Darses, S.; Genet, J.-P. J. Am. Chem. Soc. 2004, 126, 15356. (b) Mora, G.; Darses, S.; Genet, J.-P. Adv. Synth. Catal. 2007, 349, 1180.
    15) (a) Qin, C.; Chen, J.; Wu, H.; Cheng, J.; Zhang, Q.; Zuo B.; Su W.; Ding J. Tetrahedron Lett. 2008, 49, 1884. (b) Zheng, H.; Ding, J.; Chen, J.; Liu, M.; Gao W.; Wu, H. Synlett 2011, 1626.
    16) Takezawa, A.; Yamaguchi, K.; Ohmura, T.; Yamamoto, Y.; Miyaura, N. Synlett 2002, 1733.
    17) Wang, Z.; Zou, G.; Tang, J. Chem. Commun. 2004, 1192.
    18) (a) Devon, T. K.; Scott. A. I. Handbook of Naturally Occurring Compounds, Vol. 1, Academic Press, New York, 1975, pp. 249–264. (b) Elderfield, R. C. in Hetrocyclic Compounds, Vol. 2,Wiley, New York, 1951, chap. 210. (c) Beck, J. J.; Chou, S.-C. J. Nat. Prod. 2007, 70, 891. (d) Witulski, B.; Zimmermann, A.; Gowans, N. D. Chem. Commun. 2002, 2984.
    19) (a) Cowell, A.; Stille, J. K. J. Am. Chem. Soc. 1980, 102, 4193. (b) Larock, R. C.; Fellows, C. A. J. Am. Chem. Soc. 1982, 104, 1900. (c) Larock, R. C.; Fellows, C. A. J. Org. Chem. 1980, 45, 363. (d) Negishi, E. T.; Conperet, C.; Ma, S.; Lion, S. Y.; Liu, F. Chem. Rev. 1996, 96, 365. (e) Ojima, I.; Tzamarionadki, M.; Li, Z.; Donovan, R. J. Chem. Rev. 1996, 96, 635. (f) Cho, C. S.; Baek, D. Y.; Shim, S. C. J. Heterocycl. Chem. 1999, 36, 1101. (g) Cho, C. S.; Baek, D. Y.; Shim, S. C.; Oh, D. H. Synth. Commun. 2000, 30, 1139. (h) Chan, A.; Scheidt, K. A. J. Am. Chem. Soc. 2006, 128, 4558. (i) Zhang, B.; Xu, M.-H.; Lin, G.-Q. Org. Lett. 2009, 11, 4712.
    20) Kuriyama, M.; Ishiyama, N.; Shimazawa, R.; Shirai, R.; Onomura, O. J. Org. Chem. 2009, 74, 9210.
    21) Xing, C.-H.; Liao, Y.-X.; He, P.; Hu, Q.-S. Chem. Commun. 2010, 3010.
    22) (a) Ye, Z.; Lv, G.; Wang, W.; Zhang, M.; Cheng, J. Angew. Chem. Int. Ed. 2010, 49, 3671. (b) Ye, Z.; Lv, G.; Wang, W.; Zhang, M.; Cheng, J. J. Org. Chem. 2010, 75, 6043. (c) Luo, F.; Pan, S.; Pan, C.; Qian P.; Cheng, J. Adv. Synth. Catal. 2011, 353, 320.
    23) Chang, H.-T.; Jeganmohan, M.; Cheng, C.-H. Chem. Eur. J. 2007, 13, 4356.
    24) (a) Lin, P.-S.; Jeganmohan, M.; Cheng, C.-H. Chem. Asian J. 2007, 2, 1409. (b) Wang, C.-C.; Lin, P.-S.; Cheng, C.-H. J. Am. Chem. Soc. 2002, 124, 9696. (c) Wong, Y.-C.; Parthasarathy, K.; Cheng, C.-H. J. Am. Chem. Soc. 2009, 131, 18252. (d) Mannathan, S.; Cheng, C.-H. Chem. Commun. 2010, 46, 1923.
    25) Karthikeyan, J.; Jeganmohan, M.; Cheng, C.-H. Chem. Eur. J. 2010, 16, 8989.

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