臺灣博碩士論文加值系統

本研究製備出以吲哚為架構的氮磷鍵二級氧化磷配位基C8NP(=O)(tBu)(H) (4a) 、MeC8NP(=O)(tBu)(H) (4b)、PhC8NP(=O)(tBu)(H)(4c)。並使用X-ray單晶繞射法鑑定分子(C8N)2P(tBu) (3a'')、PhC8NPCl(tBu)(3c)、PhC8NP(=O)(tBu)(H) (4c)及[(4a'')(4a''-H+)Pd(μ-Cl)]2 (5a)等結構。吲哚的結構具有穩定金屬的特性，能成功的穩定金屬錯合物。二級氧化磷基具有在空氣與水氣下穩定的特性，有利於保存。嘗試將C8NP(=O)(tBu)(H) (4a)、MeC8NP(=O)(tBu)(H) (4b)、PhC8NP(=O)(tBu)(H)(4c)應用在 Suzuki-Miyaura 耦合反應上，不論對於離去基為溴或氯的反應物，皆能適用於多種官能基，且有不錯的催化效果。

Several new indolyl secondary phosphine oxides C8NP(=O)(tBu)(H) (4a), MeC8NP(=O)(tBu)(H) (4b), and PhC8NP(=O)(tBu)(H) (4c) were prepared. The molecular structures of (C8N)2P(tBu) (3a''), PhC8NPCl(tBu) (3c), PhC8NP(=O)(tBu)(H) (4c) and [(4a'')(4a''-H+)Pd(μ-Cl)]2 (5a) were determined by single-crystal X-ray diffraction methods. The structure of palladium complex is stabilized by the indolyl scafford. In addition, secondary phosphine oxides were air- and moisture-stable preligands and advantageous for the purpose of storage. In this work, the ligand C8NP(=O)(tBu)(H) (4a), MeC8NP(=O)(tBu)(H) (4b) and PhC8NP(=O)(tBu)(H) (4c) were employed in the Suzuki-Miyaura cross-coupling reaction. The catalytic system showed good tolerance of functional groups and also found to catalyze the coupling reactions of aryl bromides and less reactive aryl chlorides.

第一章 序論 ……………………………………………………………2
第一節 耦合反應 ………………………………………………………3
第二節 Suzuki-Miyaura 耦合反應 ……………………………………5
第三節 配位基的簡介…………………………………………………10
第四節 二級氧化磷基的簡介…………………………………………14
第五節 氮-磷鍵磷配位基 ……………………………………………16
第六節 研究動機………………………………………………………19

第二章 結果與討論……………………………………………………21
第一節 氮磷鍵（N-P）配位基4的製備及鑑定…………………22
第二節 含鈀金屬氮磷鍵（N-P）錯合物5a的製備及鑑定……33
第三節 配位基4應用於Suzuki耦合反應催化芳香基溴化物…37
第四節 配位基4應用於Suzuki耦合反應催化芳香基氯化物 …47

第三章 結論……………………………………………………………52

第四章 實驗……………………………………………………………53
第一節 儀器與藥品……………………………………………………54
第二節 操作技巧………………………………………………………58
第三節 合成與鑑定……………………………………………………59
第四節 Suzuki耦合反應步驟…………………………………………65

參考文獻…………………………………………………………………70

附錄………………………………………………………………………74
光譜數據…………………………………………………………………75
晶體數據…………………………………………………………………91
耦合產物數據…………………………………………………………130

1. (a) Yin, L. X.; Liebscher, J. Chem. Rev. 2007, 107, 133-173. (b) Corbet, J.-P.; Mignani, G. Chem. Rev. 2006, 106, 2651-2710. (c) Roglans, A.; Pla-Quintana, A.; Moreno-Manas, M. Chem. Rev. 2006, 106, 4622-4643. (d) Bhayana, B.; Fors, B. P.; Buchwald, S. L. Org. Lett. 2009, 11, 3954-3957. (e) Nicolaou, K. C.; Bulger, P. G.; Sarlah, D. Angew. Chem. Chem. Int. Ed. 2005, 44, 4442-4489. (f) Walker, S.D.; Barder, T. E.; Martinelli, J. R.; Buchwald, S. L. Angew. Chem. Int. Ed. 2004, 43, 1871-1876.
2. (a) Harkal,S.; Rataboul, F.; Zapf, A.; Fuhrmann, C.; Riermeier, T. H.; Monsees, A.; Beller, M. Adv. Synth. Catal. 2004, 346, 1742-1748.
(b) Wolfe, J. P.; Buchwald, S. L. Angew. Chem. Int. Ed. 1999, 38, 2413.
3. Filler, M. A.; Musgrave, C. B.; Bent, S. F. J. Phys. Chem. C. 2007, 111, 1739-1743.
4. (a) Brauer, D. J.; Hingst, M.; Kottsieper, K. W.; Liek, C.; Nickel, T.; Tepper, M.; Stelzer, O.; Sheldrick, W. S. J. Organomet. Chem. 2002, 645, 14-26. (b) Zhao, D.; Mao, L.; Wang, Y.; Yang, D.; Zhang Q.; Wang. R. Org. Lett. 2010, 12, 1880-1882.
5. (a) Barder, T. E.; Walker, S. D.; Martinelli, J. R.; Buchwald, S. L. J. Am. Chem. Soc. 2005, 127, 4685-4696. (b) Marion, N.; Navarro, O.; Mei, J.; Stevens, E. D.; Scott, N. M.; Nolan, S. P. J. Am. Chem. Soc. 2006, 128, 4101-4111.
6. D’Aprano, G.; Leclerc, M.; Zotti, G.; Schiavon, G., Chem. Mater., 1995, 7, 33-42.
7. Pla, D.; Marchal, A.; Olsen, C. A.; Francesch, A.; Cuevas, C.; Albericio, F.; Alvarez, M. J. Med. Chem. 2006, 49, 3257-3268.
8. Yuan, Y.; Men, H.; Lee, C. J. Am. Chem. Soc. 2004, 126, 14720-14721.
9. (a) Stille, J. K. Angew. Chem. Int. Ed. 1986, 25, 508. (b) Miyaura, N. Top. Curr. Chem. 2002, 219, 11-59. (c) Suzuki, A. in Modern Arene Chemistry (Ed. by D. Astruc), Wiley-VCH, Weinheim, 2002, pp. 53 – 106. (d) Negishi, E.-i.; Zeng, X.; Tan, Z.; Qian, M.; Hu, Q.; Huang, Z. in Metal-Catalyzed Cross-Coupling Reactions, 2nd ed. (Eds. by A. de Meijere, F. Diederich), Wiley-VCH, Weinheim, 2004, chap. 15. (e) Hayashi, T.; Konishi, M.; Kobori, Y.; Kumada, M.; Higuchi, T.; Hirotsu, K. J. Am. Chem. Soc. 1984, 106, 158-163. (f) Hiyama, T. J.Organomet. Chem. 2002, 653, 58-61. (g) Denmark, S. E.; Sweis, R. F. Acc. Chem. Res. 2002, 35, 835-846.
10. Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457-2483.
11. Atkinson, R. C.; Gibson, V. C.; Long, N. J. Chem. Rev. 2004, 33, 313-328.
12. Molander, G. A. ,Felix, L. A. J. Org. Chem. 2005, 70, 3950-2956.
13. Suzuki, A. J. Organomet. Chem. 1999, 576, 147-168.
14. Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457-2483.
15. Matos, K.; Soderquist, J. A. J. Org. Chem. 1998, 63, 461-470.
16. (a) Nicolaou, K. C.; Boddy, C. N. C.; Brase, S.; Winssinger. N. Angew. Chem. Int. Ed.1999, 38, 2096. (b) Baudoin, O.; Gueitte, F. in Studies in Natural Product Chemistry, Vol. 29 (Ed. by A.-U. Rahman) Elsevier, Amsterdam, 2003, pp. 355 –418. (c) Bringmann, G.; Pokorny, F. in The Alkaloids, Vol. 46 (Ed. by G. A. Cordell), Academic Press, New York, 1995, pp. 127 –271.
17. Parr, R. G.; Pearson, R. G. J. Am. Chem. Soc. 1983, 105, 7512-7516.
18. Berthod, M.; Mignani, G.; Woodward, G.; Lemaire, M. Chem. Rev. 2005, 105, 1801-1836.
19. Ackermann, L.; Potukuchi, H.K.; lthammer, A.A; Born, R.; Mayer, P. Org.Lett. 2010, 12, 1004-1007.
20. (a) Lira, R.; Wolfe, J. P. J. Am. Chem. Soc. 2004, 126, 13906-13907. (b) Miura, M. Angew. Chem. Int. Ed. 2004, 43, 2201-2203.
21. Schaarschmidt, D.; Lang, H. ACS Catal. 2011, 1, 411–416.
22. Hoshi, T.; Nakazawa, T.; Saitoh, I.; Mori, A.; Suzuki, T.; Sakai, J.-i.; Hagiwara, H. Org. Lett. 2008, 10, 2063-2066.
23. Wei, C.-H.; Wu, C.-E. Huang, Y.-L., Kultyshev, R. G.; Hong, F.-E. Chem. Eur. J. 2007, 13, 1583-1593.
24. Jung, L.-Y.; Tsai, S.-H. ; Hong, F.-E. Organometallics 2009, 28, 6044–6053.
25. Hu, D.-F.; Weng, C.-M.; Hong, F.-E. Organometallics 2011, 30, 1139–1147.
26. Ghosh, R.; Adarsh, N. N.; Sarkar, A. J. Org. Chem. 2010, 75, 5320-5322.
27. So, C. M.; Lau, C. P. Kwong, F. Y. Org. Lett. 2007, 9, 2795-2798.
28. Moloy, K. G.; Petersen, J. L. J. Am.Chem. Soc. 1995, 117, 7696.