臺灣博碩士論文加值系統

有效利用二價鈀金屬錯合物催化2-苯基吡啶鄰位位置的碳-氫鍵活化及其一系列的吡啶衍生物與有機三氟硼酸鉀鹽試劑進行偶合反應。最佳的反應條件為2-苯基吡啶及其吡啶衍生物在10 mol % Pd(OAc)2、3當量醋酸銅(氧化試劑)、2當量對-苯二酮(助氧化劑)與2.5當量的芳香基三氟硼酸試劑進行反應， 溶於1,4二氧六環中，溫度為120 oC，反應時間為24小時。在本研究中發現，芳香基三氟硼酸鉀鹽試劑取代基不管是推電子或為拉電子基，對反應的效應的影響並無太大的差異。本研究中對-苯二酮所扮演的角色為一助氧化劑可提升二價鈀金屬錯合物的陰離子做轉移金屬化之還原消去( Transmetallation-Reductive Elimination ) 步驟；另外本研究也做了動力學同位素效應 ( kH/kD ) 的探討，得到kH/kD為1.09，所代表的意義為碳-氫鍵的斷裂並非反應速率決定步驟。

An efficient one-pot synthesis of ortho arylated 2-phenylpyridine and pyridine derivatives with potassium aryltrifluoroborates is presented. The optimal reaction conditions are as follows: 2-phenylpyridine and pyridine derivatives were treated with two and a half equivalents of potassium aryltrifluoroborates in the presence of 10 mol % Pd(OAc)2, three equivalents of Cu(OAc)2, two equivalents of p-benzoquinone in 1,4-dioxane at 120 oC for 24 h. p-Benzoquinone is an essential co-oxidant and promoter in the transmetallation-reductive elimination step. The kinetic isotope effect (kH/kD) for the C-H bond activation was determined to be 1.09.

表目錄 ------------------------------------------------------------------------ I
圖目錄 ------------------------------------------------------------------------ II
摘要 ------------------------------------------------------------------------III
第一章 1.1前言--------------------------------------------------------------1
1.1.1 Suzuki-Miyaura 反應簡介---------------------------------1
1.1.2 Suzuki-Miyaura 反應之機制------------------------------3
1.1.3 催化劑類型--------------------------------------------------5
1.1.4 鹼的類型-----------------------------------------------------7
1.1.5 偶合試劑類型-----------------------------------------------7
1.1.6 近期 Suzuki- Miyaura 反應類型-----------------------12
1.2 研究動機------------------------------------------------------17
第二章 二價鈀金屬錯合物催化2-苯基吡啶及吡啶衍生物與有機三氟硼酸鉀鹽試劑進行鄰位碳-氫鍵活化/碳-碳鍵加成反應
2.1結果與討論----------------------------------------------------19
2.1.1 反應條件對結果的影響-------------------------------- 19
2.1.2 反應機制的探討-------------------------------------------25
2.1.3 不同起始物對結果之影響-----------------------------26
2.1.4 不同有機硼酸試劑之比較-------------------------------33
2.1.5 動力學同位素效應----------------------------------------35
2.1.6 不同有機硼酸試劑與醯胺反應-------------------------36

2.2 結論------------------------------------------------------------37
第三章 實驗部份與光譜資料
3.1實驗部份及光譜資料----------------------------------------38
參考文獻 ------------------------------------------------------------------------63
附錄 ------------------------------------------------------------------------67

1.(a) H. A. Chiong, Q.-N. Pham, O. Daugulis, J. Am. Chem. Soc. 2007, 129, 9879; (b) D. R. Stuart, E. Villemure, K. Fagnou, J. Am. Chem. Soc. 2007, 129, 12072; (c) G. Cai, Y. Fu, Y. Li, X. Wan, Z. Shi, J. Am. Chem. Soc. 2007, 129, 7666; (d) K. L. Hull, M. S. Sanford, J. Am. Chem. Soc. 2007, 129, 11904; (e) T. A. Dwight, N. R. Rue, D. Charyk, R. Josselyn, B. DeBoef, Org. Lett. 2007, 9, 3137; (f) J.-B. Xia, S.-L. You, Organometallics 2007, 26, 4869; (g) K. L. Hull, E. L. Lanni, M. S. Sanford, J. Am. Chem. Soc. 2006, 128, 14047.
2. (a)S. Kirchberg, T. Vogler, A. Studer, Synlett 2008, 2841; (b) T. Vogler, A. Studer, Org. Lett. 2008, 10, 129; (c) S. D. Yang, C.-L. Sun, Z. Fang, B.-J. Li, Y.-Z. Li, Z.-J. Shi, Angew. Chem. Int. Ed. 2008, 47, 1473; (d) D.-H. Wang, M. Wasa, R. Giri, J.-Q. Yu, J. Am. Chem. Soc. 2008, 130, 7190; (e) B.-F. Shi, N. Maugel, Y.-H. Zhang, J.-Q. Yu, Angew. Chem. Int. Ed. 2008, 47, 4882; (f) J.-H. Chu, C.-C. Chen, M.-J. Wu, Organometallics 2008, 27, 5173; (g) Z. Shi, B. Li, X. Wan, J. Cheng, Z. Fang, B. Cao, C. Qin, Y. Wang, Angew. Chem. Int. Ed. 2007, 46, 5554; (h) R. Giri, N. Maugel, J. J. Li, D. H. Wang, S. P Breazzano, L. B. Saunders, J. Q. Yu, J. Am. Chem. Soc. 2007, 129, 3510; (i) X. Chen, C. E. Goodhue, J.-Q. Yu, J. Am. Chem. Soc. 2006, 128, 12634; (j) F. Kakiuchi, M. Usui, S. Ueno, N. Chatani, S. Murai, J. Am. Chem. Soc. 2004, 126, 2706. (k) F. Kakiuchi, S. Kan, K. Igi, N. Chatani, S. Murai, J. Am. Chem. Soc. 2003, 125, 1698.
3. (a) X. Chen, J. J. Li, X. S. Hao, C. E. Goodhue, J. Q. Yu, J. Am. Chem. Soc. 2006, 128, 78. (b) S. Oi, S. Fukita, Y. Inoue, Chem. Commun. 1998, 2439; (c)J. Norinder, A. Matsumoto, N. Yoshikai, E. Nakamura, J. Am. Chem. Soc. 2008, 130, 5858.
4. N. Miyaura, T. Yanagi, A. Suzuki, Synth. Commun. 1981, 11, 513.
5. (a) M. S. Wong, X. L. Zhang, Tetrahedron Lett. 2001, 42, 4087; (b) M. Moreno-Manas, M. Perez, R. Pleixats, J. Org. Chem. 1996, 61, 2346.
6. (a) S. Darses, J.-P. Genet, Chem. Rev. 2008, 108, 288; (b) G. A. Molander, N. Ellis, Acc. Chem. Res. 2007, 40, 275; (c) H. A. Stefani, R. Cella, A. S. Vieira, Tetrahedron 2007, 63, 3623.
7. G. A. Molander, B. Biolatto, J. Org. Chem. 2003, 68, 4302.
8. (a) J. Zhao, Y. Zhang, K. Cheng, J. Org. Chem. 2008, 73, 7428; (b) H. Ge, M. J. Niphakis, G. I. Georg, J. Am. Chem. Soc. 2008, 130, 3708; (c) D.-H. Wang, T.-S. Mei, J.-Q. Yu, J. Am. Chem. Soc. 2008, 130, 17676.
9. (a) R. D. Chambers, H. C. Clark, C. Willis, J. J. Am. Chem. Soc. 1960, 82, 5298; (b) G. Pawelke, F. Heyder, H. B?嫠rger, J. Organomet. Chem. 1979, 178, 1; (c) G. Bir, W. Schacht, D. Kaufmann, J. Organomet. Chem. 1988, 340, 267.
10. E. Vedejs, R. W. Chapman, S. C. Fields, S. Lin, M. R. Schrimpf, J. Org. Chem. 1995, 60, 3020.
11. N. Miyaura, A. Suzuki, Chem. Rev. 1995, 95, 2457.
12. M. Beller, H. Fischer, W. A. Herrmann, K. Öfele, C. Brossmer, Angew. Chem., Int. Ed. Engl. 1995, 34, 1848.
13. H. Weissman, D. Milstein, Chem. Commun. 1999, 1901.
14. (a) R. B. Bedford, C. S. J. Cazin, J. Chem. Soc. Chem. Commun. 2001, 1540; (b) S. J. Coles, T. Gelbrich, P. N. Horton, M. B. Hursthouse, M. E. Light, Organometallics 2003, 22, 987.
15. Z. Xiong, N. Wang, M. Dai, A. Li, J. Chen, Z. Yang, Org Lett. 2004, 6, 3337.
16. D. Zim, A. S. Gruber, G. Ebeling, J. Dupont, A. L. Monteiro, Org. Lett. 2000, 2, 2881.
17. S. Gibson, D. F. Foster, G. R. Easthem, R. P. Tooze, D. C. Hamilton, J. Chem. Commun. 2001, 779.
18. A. A. C. Brage, N. H. Morgon, G. Ujaque, F. Maseras, J. Am. Chem. Soc. 2005, 127, 9298.
19. G. Altenhoff, R. Goddard, C. W. Lehmann, F. Glorius, Angew. Chem., Ine. Ed. 2003, 42, 3690.
20. Y. M. Kim, S. Yu, J. Am. Chem. Soc. 2003, 125, 1696.
21. K. L. Billingsley, K. W. Anderson, S. L. Buchwald, Angew. Chem., Ine. Ed. 2006, 45, 3484.
22. N. Kudo, M. Perseghini, G. C. Fu, Angew. Chem., Ine. Ed. 2006, 45, 1282.
23. K. L. Billingsley, T. E. Barder, S. L. Buchwald, Angew. Chem., Ine. Ed. 2007, 46, 5359.
24. (a) G. A. Molander, M. R. Rivero, Org. Lett. 2002, 4, 107; (b) G. A. Molander, C. R. Bernardi, J. Org. Chem. 2002, 67, 8424.
25. (a) G. A. Molander, B. W. Katona. F. Machrouhi, J. Org. Chem. 2002, 67, 8416; (b) G. A. Molander, C. S. Yun, M. Ribagorda, B. Biolatto, J. Org. Chem. 2003, 68, 5534.
26. S. D. Walker, T. E. Barder, J. R. Martinelli, S. L. Buchald, Angew. Chem. Ine. Ed. 2004, 43, 1871.
27. M. C. Willis, L. H. W. Powell, C. K. Claverie, S. J. Watson, Angew. Chem. Ine. Ed. 2004, 43, 1249
28. A. Zapf, A. Ehrentraut, M. Beller, Angew. Chem. Ine. Ed. 2000, 39, 4153.
29. P. R. Parry, C. Wang. A. S. Batsanov, M. R. Bryce, B. Tarbit, J. Org. Chem. 2002, 67, 7541.
30. Z. Shi, B. Li, X. Wan, J. Cheng, Z. Fang, B. Cao, C. Qin, Y. Wang, Angew. Chem. Ine. Ed. 2007, 46, 5554.
31. (a) V. V. Namboodiri, R. S. Varma, Green Chem. 2001, 3, 146; (b) Y. Gong, W. He, Org Lett. 2004, 6, 3808; (c) Y. Wang, D. R. Sauer, Org Lett. 2004, 6, 2793.
32. (a) W. Zhang, C. H. T. Chen, Y. Lu, T. Nagashima, Org Lett. 2004, 6, 1473; (b) B. Basu, P. Das, M. H. Bhuiyan, S. Jha, Tetrahedron Lett. 2003, 44, 3817; (c) G. Miao, P. Ye, L. Yu, C. M. Baldino, J. Org. Chem. 2005, 70, 2332.
33. (a) R. K. Arvela, N. E. Leadbeater, M. J. Collins, Tetrahedron 2005, 61, 9349; (b) R. K. Arvela, N. E. Leadbeater, L. T. Mack, C. M. Kormos, Tetrahedron Lett. 2006, 47, 217; (c) N. E. Leadbeater, R. J. Smith, Org Lett. 2006, 8, 4589.
34. G. W. Kabalka, R. M. Pagni, M. Hair, Org Lett. 1999, 1, 1423.