臺灣博碩士論文加值系統

本研究將二級氧化磷基(Secondary phosphine oxides, 1a-b)和亞胺(Imines, 2a-2h)分別與不同金屬鈀試劑反應形成多個金屬鈀錯合物(palladium complexes A-C)，其中金屬鈀錯合物C在同樣的養晶條件下卻得到取代基有兩種角度的晶體結構。由於二級氧化磷基具有在空氣與水氣下穩定的特性，因此有利於保存，其金屬錯合物也具有相同之特性。
另外，將二級氧化磷基和亞胺作為起始物，在氧化劑(Ag2CO3)存在與溫和條件下，製備出苯醌(benzoquinone)上最多四個C-H鍵同時被活化成C-N和C-P鍵的主產物，且產率可高達90.6 %。其中Pd(OAc)2雖然不是必要的催化劑，但隨著Pd(OAc)2催化劑量的增加，主產物的產率也會增加。
萘醌(naphthoquinone)在相同條件下也可製備出兩個C-H鍵同時被活化成C-N和C-P鍵的產物。本研究並依優選條件及所得的副產物種類推導出這系列可能的反應機構。

Secondary phosphine oxides (SPOs) are air-/moisture-stable and are advantageous for the purpose of storage. They might act as preligands towards transition metals after conversion to its tautomeric form, Phosphinous Acid (PA). Palladium complexes A-C were obtained from the reactions of Pd(II) with some selected secondary phosphine oxides (SPOs) and imines. The same chemical formula of palladium complex C with two different orientations of ligands were determined by single-crystal X-ray diffraction methods.
Direct C-H functionalization of benzoquinone (BQ) was observed from the reaction of it with secondary phosphine oxides plus imines and in the presence of oxidant Ag+. Through this method, a variety of benzoquinone derivatives with both C-N and C-P bond formations on BQ were achieved in one-pot reaction and with high yields. The yields of the C-H functionalization of benzoquinone were enhanced by the extra addition of certain amount of Pd(OAc)2. Similar C-H functionalization on naphthoquinone (NQ) was also observed.
A mechanism was proposed to account for the formations of all the quinone derivatives. It is believed that the reaction does not undergo a radical reaction pathway, as reported in many related works.

謝誌………………………………………………………………………i
Abstract……………………………………………………………….ii
摘要………………………………………………………………...........iii
目錄…..………………………………………………………..………iv
Scheme 目錄………………………………...………………….…….vi
Figure 目錄……………………………………………………..…...ix
Table 目錄…………………………………………………….…….....x
第一章 前言…………………………………………………..……..1
第一節 二級氧化膦基(Secondary phosphine Oxide; SPO)簡介...2
第二節 C-H鍵活化反應(C-H functionalization reaction)簡介.....7
第三節 1,4-苯醌 (p-Benzoquinone)上C-H鍵活化反應……...…..10
第四節 研究方向……………..…………………………………....15
第二章 結果與討論…………………………………………………..17
第一節 二級氧化磷基的製備. …………………………………18
第二節 亞胺(Imine)的製備………………………………………..19
第三節 金屬鈀錯合物之合成與晶體鑑定………………………..20
第四節 Benzoquinone上C-H鍵活化反應與反應機制….…...…..27
第五節 Naphthoquinone上C-H鍵活化反應………………….…56
第三章 結論…………………………………………………………..60
第四章 實驗部分……………………………………………………..62
第一節 儀器………………………………………………………..63
第二節 藥品……………………………………………..…………66
第三節 合成與鑑定…………………………………..…………....69
第五章 參考文獻……………………………………………………92
第六章 附錄…………………………………………………………96
第一節 反應產物光譜圖譜………………….…………………97
第二節 晶體數據………………………………………………156

1.(a) Liu, Y.; Cao, Z.; Du, H. J. Org. Chem. 2012, 77, 4479-4483. (b) Qin, C.; Lu, W. J. Org. Chem. 2008, 73, 7424-7427.
2.Williams, R. H.; Hamilton, L. A. J. Am. Chem. Soc., 1952, 74, 5418-5420.
3.Shaikh, T. M.; Weng, C. M.; Hong, F. E. Coord. Chem. Rev. 2012, 256, 771-803.
4.Beaulied, W. B.; Rauchfuss, T. B.; Roundhill, D. M. Inorg. Chem., 1975, 14, 1732-1734.
5.Li, G. Y. Angew. Chem. Int. Ed., 2001, 40, 1513-1516.
6.Ackermann, L. Org. Lett., 2005, 7, 3123-3125.
7.Wei, C. H.; Wu, C. E.; Huang, Y. L.; Kultyshev, R. G.; Hong, F. E. Chem. Eur. J., 2007, 13, 1583-1593.
8.Hu, D. F.; Weng, C. M.; Hong, F. E. Organometallics, 2011, 30, 1139-1147.
9.Chang, Y. C.; Chang, W. C.; Hu, C. Y.; Hong, F. E. Organometallics, 2014, 33, 3523-3534.
10.Chang, T.W.; Ho, P.Y.; Mao, K.C.; Hong, F. E. Dalton Trans., 2015, 44, 17129-17142.
11.Kalek, M.; Johansson, T.; Jezowska, M.; Stawinski, J. Org. Lett., 2010, 12, 4702-4704.
12.Wang, T.; Sang, S.; Liu, L.; Qiao, H.; Gao, Y.; Zhao, Y. J. Org. Chem., 2014, 79, 608-617.
13.洪豐裕，《有機金屬化學》。國立國立中興大學出版中心，華藝學術出版社，2015。
14.Ye, J.; Lautens, M. Nature Chemistry, 2015, 7, 863-870.
15.Catellani, M.; Frignani, F.; Rangoni, A. Angew. Chem. Int. Ed. Engl., 1997, 36, 119-122.
16.Dong, Z.; Dong, G. J. Am. Chem. Soc., 2013, 135, 18350-18353.
17.Dong, Z.; Dong, G. J. Am. Chem. Soc., 2013, 137, 5887-5890.
18.Weinstabl, H.; Suhartono, M.; Qureshi, Z.; Lautens, M. Angew. Chem. Int. Ed., 2013, 52, 5305-5308.
19.Decharin, N.; Stahl, S. S. J. Am. Chem. Soc. 2011, 133, 5732-5735.
20.Lyons, T. W.; Hull, K. L.; Sanford, M. S. J. Am. Chem. Soc., 2011, 133, 4455-4464.
21.Vasseur, A.; Muzart, J.; Bras, J. L. Eur. J. Org. Chem., 2015, 19, 4053-4069.
22.Hull, K. L.; Sanford, M. S. J. Am. Chem. Soc., 2007, 129, 11904-11905.
23.Lin, Y. S.; McKelvey, W.; Waidyanatha, S.; Rappaport, S. M. Biomarkers., 2006, 11, 14-27.
24.Thomson, R. H. Pharm. Weekbl. Sci., 1991, 13, 70-73.
25.Patai, S.; Rappaport, Z. The Chemistry of Quinonoid Compounds, Vol II, Wiley: New York, 1988.
26.Koyama, J. Recent Pat. Anti-Infect. Drug Discovery, 2006, 1, 113-125.
27.Brien, J. O’P. Chem. Biol. Interact., 1991, 80, 1-41.
28.Dowd, P.; Zheng, Z. B. Proc. Natl. Acad. Sci., 1995, 92, 8171-8175.
29.Gonzalez-Ibarra, M.; Farfan, N.; Trejo, C.; Uribe, S.; Lotina-Hennsen, B. J. Agric. Food Chem., 2005, 53, 3415-3420.
30.Watson, J. A.; Pascal, R. A.; Ho, D. M.; Kilway, K. V. Tetrahedron Lett., 2000, 41, 5005-5008.
31.Gan, X.; Jiang, W.; Wang, W.; Hu, L. Org. Lett., 2009, 11, 589-592.
32.Fujiwara, Y.; Domingo, V.; Seiple, I. B.; Gianatassio, R.; Bel, M. D.; Baran, P. P. S. J. Am.Chem. Soc., 2011, 133, 3292-3295.
33.Lisboa, C. S.; Santos, V. G.; Vaz, B. G.; Lucas, N. C.; Eberlin, M. N.; Garden, S. J. J. Org. Chem., 2011, 76, 5264-5273.
34.Walker, S. E.; Jordan-Hore, J. A.; Johnson, D. G.; Macgregor, S. A.; Lee, A. L. Angew. Chem. Int. Ed., 2014, 53, 13876-13879.
35.Deng, H. P.; Wang, D.; Szabo’, K. J. J. Org. Chem., 2015, 80, 3343-3348.
36.Zhang, C.; McClure, J.; Chou, C. J. J. Org. Chem., 2015, 80, 4919-4927.
37.Hull, K. L.; Sanford, M. S. J. Am. Chem. Soc. 2007, 129, 11904-11905.
38.Zhang, C.; McClure, J.; Chou, C. J. J. Org. Chem. 2015, 80, 4919-4927.
39.Li, G. Y. J. Org. Chem. 2002, 67, 3643-3650.
40.Azizi, K.; Karimi, M.; Heydari, A. Tetrahedron. 2014, 55, 7236-7239.
41.Vasseur, A.; Muzart, J.; Bras, J. L. Eur. J. Org. Chem., 2015, 19, 4053-4069.
42.Palma, A.; Cardenas, J.; Frontana-Uribe, B. A. Green Chem. 2009, 11, 283-293.
43.Park, J. G.; Jeon, I.G.; Harris, T. D. Inorg. Chem. 2015, 54, 359-369.
44.Barbosa, L. C.; Pereira, U. A.; Maltha, C. R.; Teixeira, R. R.; Valente, M.; Oliveira, F. J. R.; Costa, L. V.; Moraes, M. O.; Pessoa, C. Molecules. 2010, 15, 5629-5643.