臺灣博碩士論文加值系統

利用鈀金屬和其他過渡金屬催化末端炔與芳香基鹵化物的耦合反應又稱為Sonogashira 耦合反應，近年來被廣泛地運用在碳-碳鍵的生成上，是最常被用來合成炔類化合物的方法。在論文的第一部分，我們發現銅錯合物CuI(Xantphose) 可以當作有效率的催化劑，在微波加熱下可以有效促進末端炔類與芳香基鹵化物及乙烯基鹵烷的耦合反應，並能在短時間內得到高產率的多樣性炔類化合物。
而論文的第二部分，我們將探討銠金屬和銅金屬催化碳-硫鍵的生成反應。我們發現微波加熱可以有效的促進芳香基鹵化物和芳香基硫醇之交互耦合反應。

The coupling of aryl halides with terminal alkynes catalyzed by palladium and copper is commonly called Sonogashira cross-coupling reaction.This method is one of the most important ways to prepare internal alkynes. In the first part of this thesis, we found CuI(xantphose) can be used as an efficient catalyst under the microwave, promoted coupling reaction of aryl or vinyl halides with terminal alkynes to provide the corresponding alkynes and enynes with excellent yields in short reaction time.
In the second part, we will study the rhodium and copper-catalyzed carbon-sulfur bond formation under microwave heating.

摘 要…………………………………………………………………………III
Abstract………………………………………………………………………IV
表目錄…………………………………………………………………………VII
圖目錄………………………………………………………………………VIII
一、序論
(一)過渡金屬催化之交互耦合反應…………………………………1
(二)Sonogashira Type 耦合反應……………………………………4
(三)碳硫鍵交互耦合反應……………………………………………12
二、研究動機
(一) 微波促進銅金屬催化Sonogashira類型耦合反應………..….…..21
(二) 微波促進碳-硫鍵生成…………………………………….………22
三、結果與討論
(一) 微波促進銅金屬催化Sonogashira類型耦合反應………………23
(二) 結果與展望………………………………………………………31
(三) 微波促進碳-硫鍵生成…………………………………………….32
(四) 結果與展望………………………………………………………45
四、儀器設備與藥品溶劑…………………………………………………46
五、實驗步驟………………………………………………………………48
六、光譜數據………………………………………………………………52
七、參考資料………………………………………………………………118
八、NMR 光譜……………………………………………………………122

1.Heck, R. F.; Negishi, E.; Suzuki, A. Nobelprize.Org. 2010.
2.Kumada, M.; Tamao, K.; Yamamoto, K.; Kiso, Y. J. Am. Chem. Soc. 1972,
94, 4373-4374.
3.Heck, R. F.; Nolley, J. P. J. Org. Chem., 1972, 37, 2320-2322.
4.Negishi, E.; King, A. O. J. Org. Chem. 1978, 43, 358-360.
5.(a)Milstein, D.; Stille, J. K. J. Am. Chem. Soc. 1978, 100, 3636-3638. (b) Milstein, D.; Stille, J. J. Am. Chem. Soc. 1979, 101, 4992-4998. (c) Scott, W. J.; Stille, J. K. J. Am. Chem. Soc. 1986, 108, 3033-3040. (d) Echavarren, A. M.; Stille, J. K. J. Am. Chem. Soc. 1987, 109, 5478-5486. (e) Stille, J. K. Angew. Chem., Int. Ed. 1986, 25, 508-524.
6.(a) Miyaura, N.; Yamada, K.; Suzuki, A. Tetrahedron Lett. 1979, 20, 3437-3440.(b) Miyaura, N.; Yanagi, T.; Suzuki, A. Synth. Commun. 1981, 11, 513-519.(c) Miyaura, N.; Yamada, K. J. Am. Chem. Soc. 1985, 107, 972-980.(d) Miyaura, N.; Ishiyama, T.; Sasaki, H.; Ishikawa, M.; Sato, M.; Suzuki, A. J. Am. Chem. Soc. 1989, 111, 314-321.(e) Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457-2483.
7.(a) Guram, A. S.; Rennels, R. A.; Buchwald, S. L. Angew. Chem., Int. Ed. 1995, 34, 1348-1350. (b) Wolfe, J. P.; Wagaw, S.; Buchwald, S. L. J. Am. Chem. Soc. 1996, 118, 7215-7216. (c) Wolfe, J. P.; Wagaw, S.; Marcoux, J. F.; Buchwald, S. L. Acc. Chem. Res. 1998, 31, 805-818. (d) Louie, J.; Hartwig, J. F. Tetrahedron Lett. 1995, 36, 3609-3612. (e) Driver, M. S.; Hartwig, J. F. J. Am. Chem. Soc. 1996, 118, 7217-7218. (f) Hartwig, J. F. Acc. Chem. Res. 1998, 31, 852-860. (g) Shen, Q.; Hartwig, J. F. Org. Lett. 2008, 10, 4109-4112.
8.Burgos, C. H.; Barder, T. E.; Huang, X.; Buchwald, S. L. Angew. Chem., Int. Ed. 2006, 45, 4321-4326.
9.(a) Nicolaou, K. C.; Smith, A. L. Modern Acetylene Chemistry 1995. (b) Sonogashira, K. Handbook of Organopalladium Chemistry for Organic Synthesis 2002, 493-529. (c) Negishi, E.; Xu, C. Handbook of Organopalladium Chemistry for Organic Synthesis 2002, 531-549.
10.Stephens, R. D.; Castro, C. E. J. Org. Chem. 1963, 28, 3313-3315.
11.Cassar, L. J. Organomet. Chem., 1975, 93, 253-257.
12.Dieck, H.; Heck, F. J. Organomet. Chem., 1975, 93, 259-263.
13.Sonogashira, K.; Tohda, Y.; Hagihara, N. Tetrahedron Lett., 1975, 16, 4467-4470.
14.Okuro, K.; Furuune, M.; Enna, M.; Miura, M.; Nomura, M. J. Org. Chem. 1993,58, 4716-4721.
15.Monnier, F.; Turtaut, F.; Duroure L.; Taillefer, M. Org. Let. 2008, 10, 15, 3203-3206.
16.Li, P.; Wang, L. Synlett 2006, 14, 2261-2265.
17.Camino, G. A.; Alberto, A.; Avelino C.; Hermenegildo, G.; Marta, I.; Felix, S. Angew. Chem. Int. Ed. 2007, 46, 1536-1538.
18.Li, P.; Wang, L.; Wang, M.; You, F. Eur. J. Org. Chem. 2008, 5946-5951.
19.Carril, M.; Correa, A.; Bolm, C. Angew. Chem. 2008, 120, 4940-4943.
20.Hatakeyama, T.; Okada, Y.; Yoshimoto, Y; Nakamura, M. Angew. Chem. Int. Ed. 2011, 50, 10973-10976.
21.Borah, H. N.; Prajapati, D.; Boruah, R. C. Synlett 2005, 18, 2823-2825.
22.Park, S.; Kim, M.; Koo, D. H.; Chang, S. Adv. Synth. Catal. 2004, 346, 1638-1640.
23.Bertus, P.; Pale, P. J. Organomet. Chem. 1998, 567, 173-180.
24.Dillinger, S.; Bertus, P.; Pale, P. Org. Lett. 2001, 3,1661-1664.
25.Silveira, C. C.; Braga, A. L.; Vieira, A. S.; Zeni, G. J. Org. Chem. 2003, 68, 662-665.
26.Bates, C. G.; Saejueng, P.; Venkataraman, D. Org. Lett. 2004, 6, 1441-1444.
27.Hatakeyama, T.; Yoshimoto, Y.; Gabriel, T.; Nakamura, M. Org. Lett. 2008, 10, 5341-5344.
28.(a) Kaldor, S. W.; Kalish, V. J.; Davies, J. F.; Shetty, B. V.; Fritz, J. E.; Appelt, K.; Burgess, J. A.; Campanale, K. M.; Chirgadze, N. Y.; Clawson, D. K.; Dressman, B. A.; Hatch, S. D.; Khalil, D. A.; Kosa, M. B.; Lubbehusen, P. P.; Muesing, M. A.; Patick, A. K.; Reich, S. H.; Su, K. S.; Tatlock, J. H. J. Med. Chem. 1997, 40, 3979-3985. (b) Nagai, Y.; Irie, A.; Nakamura, H.; Hino, K.; Uno, H.; Nishimura, H. J. Med. Chem. 1982, 25,1065-1070. (c) Wang, Y.; Chackalamannil, S.; Hu, Z.; Clader, J. W.; Greenlee, W.; Billard, W.; Binch, H.; Crosby, G.; Ruperto, V.; Duffy, R. A.; McQuade, R.; Lachowicz, J. E. Bioorg. Med. Chem. Lett. 2000, 10, 2247-2250.
29.Migita, T.; Shimizu, T.; Asami, Y.; Shiobara, J.; Kato, Y.; Kosugi, M. Bull. Chem. Soc. Jpn. 1980, 53, 1385-1389.
30.Zheng, N.; McWilliams, J. C.; Fleitz, F. J.; Armstrong III, J. D.; Volante, R. P. J. Org. Chem. 1998, 63, 9606-9607.
31.Schopfer, U.; Schlapbach, A. Tetrahedron 2001, 57, 3069-3073.
32.Itoh, T.; Mase, T. Org. Lett. 2004, 6, 24, 4587-4590.
33.(a) Fernaindez-Rodrıiguez, M. A.; Shen, Q.; Hartwig, J. F. J. Am. Chem. Soc. 2006, 128, 2180-2181. (b) Fernaindez-Rodrıiguez, M. A.; Shen, Q.; Hartwig, J. F. Chem. Eur. J. 2006, 12, 7782-7796. (c) Fernaindez- Rodrıiguez, M. A.; Hartwig, J. F. J. Org. Chem. 2009, 74, 1663-1672.
34.Percec, V.; Bae, J. Y.; Hill, D. H. J. Org. Chem. 1995, 60, 6895-6903.
35.Zhang, Y.; Ngeow, K. C.; Ying, J. Y. Org. Lett. 2007, 9, 18, 3495-3498.
36.Wong, Y. C.; Jayanth, T. T.; Cheng, C. H. Org. Lett. 2006, 8, 24, 5613-5616.
37.Reddy, V. P.; Swapna, K.; Kumar, A. V.; Rao, K. R. J. Org. Chem. 2009, 74, 3189-3191.
38.Bates, C. G.; Gujadhur, R. K.; Venkataraman, D. Org. Lett. 2002, 4, 2803-2806.
39.Kwong, F. Y.; Buchwald, S. L. Org. Lett. 2002, 4, 3517-3520.
40.Bates, C. G.; Saejueng, P.; Doherty, M. Q.; Venkataraman, D. Org. Lett. 2004, 6, 26, 5005-5008.
41.Larsson, P. F.; Correa, A.; Carril, M.; Norrby, P. O.; Bolm, C. Angew. Chem. Int. Ed. 2009, 48, 5691-5693.
42.Correa, A.; Carril, M.; Bolm, C. Angew. Chem. Int. Ed. 2008, 47, 2880-2883.
43.Wu, W. Y.; Wang, J. C.; Tsai, F. U. Green Chem. 2009, 11, 326-329.
44.Wu, J. R.; Lin, C. H.; Lee, C. F. Chem. Commun. 2009, 4450-4452.
45.Chen, G.;Xie, J.; Weng, J.; Zhu, X.; Zheng, Z.; Cai, J.; Wan, Y. Synth. Commun. 2011, 41, 3123-3133.
46.Lin, Y. Y.; Wang, Y. J.; Cheng, J. H.; Lee, C. F. Synlett 2012, 23, 930-934.
47.Li, P.; Wang, L.; Li, H. Tetrahedron 2005, 61, 8633-8640.
48.Lin, C. H.; Wang, Y. J.; Lee, C. F. Eur. J. Org. Chem. 2010, 4368-4371.
49.Chelucci, G.; Capitta, F.; Baldino, S. Tetrahedron 2008, 64, 10250-10257.
50.Bahramian, B.; Bakherad, M.; Keivanloo, A.; Bakherad, Z.; Karrabi, B. Appl. Organomet. Chem. 2011, 25, 420-423.
51.Lai, C. S.; Kao, H. L.; Wang, Y. J.; Lee, C. F., Tetrahedron Lett. 2012, 53, 4365-4367.
52.Xu, H. J.; Liang, Y. F.; Zhoua, X. F.; Feng, Y. S., Org. Biomol. Chem. 2012, 10, 2562-2568.
53.Bottino, F.; Fradullo, R.; Pappalardo, S. J. Org. Chem. 1981, 46, 2793-2795.
54.Buranaprasertsuk, P.; Chang, J. W. W.; Chavasiri, W.; Chan, P. W. H., Tetrahedron Lett. 2008, 49, 2023-2025.
55.Veerakumar, P.; Velayudham, M.; Lu, K. L.; Rajagopal, S. Catal. Sci. Technol. 2011, 1, 1512-1525.
56.Zhang, J.; Medley, C. M.; Krause, J. A.; Guan, H. Organometallics 2010, 29, 6393-6401.
57.Catanescu, C.; Chien, L. C.; Wu, S. T. Mol. Cryst. Liq. Cryst. 2004, 411, 93-102.
58.Movassagh, B.; Mossadegh, A. Synth. Commun. 2004, 34, 2337-2343.
59.Kao, H. L.; Chen, C. K.; Wang, Y. J.; Lee, C. F. Eur. J. Org. Chem. 2011, 1776-1781.
60.Xu, H. J.; Liang, Y. F.; Zhoua, X. F.; Feng, Y. S. Org. Biomol. Chem. 2012, 10, 2562-2568.