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博碩士論文 etd-0724112-112013 詳細資訊
Title page for etd-0724112-112013
論文名稱
Title
磷或胺與鈀、鎳金屬配位錯合物的耦合反應探討
On the Study of Catalytic Cross-Coupling Reactions by Amine or Phosphine Ligated Nickel and Palladium Complexes
系所名稱
Department
畢業學年期
Year, semester
語文別
Language
學位類別
Degree
頁數
Number of pages
142
研究生
Author
指導教授
Advisor
召集委員
Convenor
口試委員
Advisory Committee
口試日期
Date of Exam
2012-05-30
繳交日期
Date of Submission
2012-07-24
關鍵字
Keywords
膦胺配位基、鈀、鎳
tertiary amine phosphinoamine ligands, Kumada-Corriu coupling, β-H elimination, palladium, nickel
統計
Statistics
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中文摘要
以有機合成方法,成功的合成出三種具有三級氮的膦胺配位基,分別為1-(2-(dicyclohexylphosphino)phenyl)pyrrole (L2)、N-(2-(dicyclohexylphosphino)phenyl) morpholine (L3)、N-(2-(diisopropylphosphino)phenyl)morpholine (L4)以及參考文獻合成出o-(dicyclohexylphosphino)biphenyl (L1)當作對照組的配位基並將此四種不同的配位基,利用in situ的方式分別對鎳金屬進行Kumada-Corriu coupling反應性的測試。
將L1、L2、L3和不同的鎳金屬起始物進行Kumada-Corriu coupling的反應性測試,意外的發現,在室溫的條件下,反應以NiCl2(DME)為金屬起始物並且利用TMEDA (1.1 equiv.)當作ligand來代替phosphinoamine ligands (L1、L2、L3)的條件下,可以有效地將iododecane和hexyllmagnesium bromide進行Kumada-Corriu coupling且具有相當高的選擇性。在此新的催化條件中,利用二級碳的isopropylmagnesium chloride會使反應快速進行β-H elimination產生直線鏈烷異構化產物。
Abstract
We successfully synthesize three different tertiary amine phosphinoamine ligands, which are 1-(2-(dicyclohexylphosphino)phenyl)pyrrole (L2), N-(2-(dicyclohexylphosphino)phenyl) morpholine (L3), and N-(2-(diisopropylphosphino)phenyl)morpholine (L4) separately. With another referenced ligand o-(dicyclohexylphosphino)biphenyl (L1) as comparison and test the reactivities toward palladium and nickel by in situ method with the four different ligands.
We test Kumada-Corriu coupling reactivity of different nickel precursors to L1, L2 and L3, surprisingly, we find that under room temperature, reaction of NiCl2(DME) as precursor and TMEDA (1.1 equiv.) as ligand to replace phosphinoamine ligands (L1、L2、L3) can effectively couple iododecane with hexyllmagnesium bromide, and the catalytic condition possesses quite high selectivity. This new Ni-catalyzed cross-coupling reactions employing secondary isopropylmagnesium chloride have led to the exclusive formation of linear isomerized cross-coupling products due to reinsertion after rapid β-H elimination.
目次 Table of Contents
論文審定書 i
謝誌 ii
中文摘要 iii
英文摘要 iv
目錄 v
圖目錄 ix
表目錄 xvi
壹、磷或胺與鈀、鎳金屬配位錯合物的耦合反應探討 1
一、緒論 1
二、結果與討論 5
1. 合成2-bromobiphenyl 5
2. 合成o-(dicyclohexylphosphino)biphenyl (L1) 7
3. 合成1-(2-bromophenyl)pyrrole 8
4. 合成1-(2-(dicyclohexylphosphino)phenyl)pyrrole (L2) 9
5. 合成N-(2-bromophenyl)morpholine 10
6. 合成N-(2-(dicyclohexylphosphino)phenyl)morpholine (L3) 12
7. 合成N-(2-(diisopropylphosphino)phenyl)morpholine (L4) 13
8. Kumada-Corriu coupling 14
8a. Aryl Grignard reagents couple with aryl halides in the presence of phosphinoanime ligand (L2). 21
8b. Alkyl Grignard reagents couple with aryl halides in the presence of phosphinoanime ligand (L2). 32
8c. Aryl Grignard reagents couple with alkyl halides in the presence of phosphinoamine ligand (L2). 40
8d. Alkyl Grignard reagents couple with alkyl halides in the presence of phosphinoamine ligand (L2). 43
8e. Different reaction conditions for alkyl Grignard reagents couple with alkyl halides. 46
8f. The new Ni-catalyzed method for alkyl Grignard reagents couple with alkyl halides. 54
8g. Examine the intermediary of alkyl radicals in alkyl-alkyl coupling. 65
8h. Possible mechanism for alkyl Grignard reagents couple with alkyl halides. 71
三、結論 74
四、實驗步驟 74
1. 一般程序 74
2. 儀器 75
3. Synthesis of 2-bromobiphenyl. 75
4. Synthesis of o-(dicyclohexylphosphino)biphenyl (L1). 76
5. Synthesis of 1-(2-bromophenyl)pyrrole. 76
6. Synthesis of 1-(2-(dicyclohexylphosphino)phenyl)pyrrole (L2). 77
7. Synthesis of N-(2-bromophenyl)morpholine. 78
8. Synthesis of N-(2-dicyclohexylphosphino)phenyl)morpholine (L3). 78
9. Synthesis of N-(2-(diisopropylphosphino)phenyl)morpholine (L4). 79
10. General procedures for the Kumada-Corriu coupling. 80
11. Hexadecane. 80
五、參考文獻 80
貳、附錄 84
一、結果與討論 84
1. Oxidative addition of p-tolylbromide with Pd2(dba)3 and L2. 84
2. Mizoroki-Heck coupling 86
3. Suzuki-Miyaura coupling 92
4. Suzuki-Miyaura coupling 102
5. Cassar-Sonogashira coupling 105
6. 合成N,N-bis(4-fluorophenyl)amine 111
7. 合成bis(4-fluoro-2-bromophenyl)amine 112
8. 合成(E)-N-benzylidene-1-phenylmethanamine 112
9. 合成(E)-(4-methoxybuta-1,3-diene-2-yloxy)trimethyl silane 113
10. Nickel-catalyzed cross-coupling reaction of p-tolylbromide with Grignard reagents under Nickel/Magnesium bimetallic cooperation. 113
11. Arylation of acetone with p-chlorotoluene. 115
12. Direct arylation of benzene: C-H bond cleavage. 117
二、實驗步驟 118
1. 一般程序 118
2. 儀器 118
3. General procedures for oxidative addition of p-tolylbromide with Pd2(dba)3 and L2 in different solvents. 119
4. General procedures for the Mizoroki-Heck coupling. 119
5. General procedures for the Suzuki-Miyaura coupling. 120
6. Synthesis of [Ph-PNP]PdCl. 120
7. General procedures for the Suzuki-Miyaura coupling. 120
8. General procedures for the Cassar-Sonogashira coupling. 121
9. Synthesis of N,N-bis(4-fluorophenyl)amine. 121
10. Synthesis of bis(4-fluoro-2-bromophenyl)amine. 122
11. Synthesis of (E)-N-benzylidene-1-phenylmethanamine. 122
12. Synthesis of (E)-(4-methoxybuta-1,3-diene-2-yloxy)trimethylsilane. 122
13. General procedures for NP-ligands進行雙金屬催化反應 123
14. General procedures for -arylation of acetone with p-chlorotoluene. 123
15. General procedures for the direct arylation of benzene. 124
三、參考文獻 124
參、Spectrum Data 127
參考文獻 References
(1) Fanta, P. E. Chem. Rev. 1964, 64, 613.
(2) Fanta, P. E. Synthesis. 1974, 9.
(3) Sainsbury, M. Tetrahedron 1980, 36, 3327.
(4) Bringmann, G.; Walter, R.; Weirich, R. Angew. Chem., Int. Ed. Engl. 1990, 29, 977.
(5) Nelson, T. D.; Meyers, A. I. Tetrahedron Lett. 1993, 34, 3061.
(6) Nelson, T. D.; Meyers, A. I. J. Org. Chem. 1994, 59, 2655.
(7) Nelson, T. D.; Meyers, A. I. Tetrahedron Lett. 1994, 35, 3259.
(8) Goodbrand, H. B.; Hu, N. X. J. Org. Chem. 1999, 64, 670.
(9) Ullmann, F. Ber. Dtsch. Chem. Ges. 1903, 2382.
(10) Haldon, E.; Alvarez, E.; Nicasio, M. C.; Perez, P. J. Organometallics 2009, 28, 3815.
(11) Lindley, J. Tetrahedron 1984, 40, 1433.
(12) Goldberg, I. Ber. Dtsch. Chem. Ges. 1906, 1691.
(13) Buchwald, S. L. Acc. Chem. Res. 2008, 41, 1439.
(14) Liang, L. C.; Chien, P. S.; Lin, J. M.; Huang, M. H.; Huang, Y. L.; Liao, J. H. Organometallics 2006, 25, 1399.
(15) Sun, K.; Wang, L.; Wang, Z. X. Organometallics 2008, 27, 5649.
(16) Martin, R.; Buchwald, S. L. J. Am. Chem. Soc. 2007, 129, 3844.
(17) Vechorkin, O.; Proust, V.; Hu, X. L. J. Am. Chem. Soc. 2009, 131, 9756.
(18) Liu, N.; Wang, Z. X. J. Org. Chem. 2011, 76, 10031.
(19) Limmert, M. E.; Roy, A. H.; Hartwig, J. F. J. Org. Chem. 2005, 70, 9364.
(20) Ren, P.; Vechorkin, O.; von Allmen, K.; Scopelliti, R.; Hu, X. L. J. Am. Chem. Soc. 2011, 133, 7084.
(21) Gibson, M.; Giugliano, R. P.; Cannon, C. P.; Murphy, S. A.; Marble, S. J.; McCabe, C. H.; Antman, E. M. Circulation 2001, 104, 537.
(22) Yang, L. M.; Huang, L. F.; Luh, T. Y. Org Lett 2004, 6, 1461.
(23) Tamao, K.; Kiso, Y.; Sumitani, K.; Kumada, M. J. Am. Chem. Soc. 1972, 94, 9268.
(24) Joshi-Pangu, A.; Wang, C. Y.; Biscoe, M. R. J. Am. Chem. Soc. 2011, 133, 8478.
(25) Jana, R.; Pathak, T. P.; Sigman, M. S. Chem. Rev. 2011, 111, 1417.
(26) Old, D. W.; Wolfe, J. P.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 120, 9722.
(27) Wolfe, J. P.; Singer, R. A.; Yang, B. H.; Buchwald, S. L. J. Am. Chem. Soc. 1999, 121, 9550.
(28) Fox, J. M.; Huang, X. H.; Chieffi, A.; Buchwald, S. L. J. Am. Chem. Soc. 2000, 122, 1360.
(29) Lundgren, R. J.; Peters, B. D.; Alsabeh, P. G.; Stradiotto, M. Angew. Chem., Int. Ed. 2010, 49, 4071.
(30) Demir, A. S.; Findik, H.; Saygili, N.; Tuna Subasi, N. Tetrahedron 2010, 66, 1308.
(31) Zhang, Y. H.; Liu, L. F.; Xin, B. W. J. Org. Chem. 2006, 71, 3994.
(32) Hulcoop, D. G.; Lautens, M. Org Lett 2007, 9, 1761.
(33) Lampman, G. M., Pavia, D. L., Kriz, G. S., Vyvyan, J. R. Spectroscopy; 4th ed. ed.; Mary Finch: Belmont, CA, 2010.
(34) Wolfe, J. P.; Buchwald, S. L. J. Org. Chem. 1997, 62, 6066.
(35) Li, G. Y.; Marshall, W. J. Organometallics 2002, 21, 590.
(36) Terao, J.; Watanabe, H.; Ikumi, A.; Kuniyasu, H.; Kambe, N. J. Am. Chem. Soc. 2002, 124, 4222.
(37) Cho, S. H.; Yoon, J.; Chang, S. J. Am. Chem. Soc. 2011, 133, 5996.
(38) Phapale, V. B.; Guisan-Ceinos, M.; Bunuel, E.; Cardenas, D. J. Chem.-Eur. J. 2009, 15, 12681.
(39) Anderson, T. J.; Jones, G. D.; Vicic, D. A. J. Am. Chem. Soc. 2004, 126, 8100.
(40) Manolikakes, G.; Knochel, P. Angew Chem Int Edit 2009, 48, 205.
(41) Gerber, R.; Frech, C. M. Chem.-Eur. J. 2011, 17, 11893.
(42) Rosen, B. M.; Quasdorf, K. W.; Wilson, D. A.; Zhang, N.; Resmerita, A. M.; Garg, N. K.; Percec, V. Chem. Rev. 2011, 111, 1346.
(43) Liu, L. F.; Zhang, Y. H.; Xin, B. W. J. Org. Chem. 2006, 71, 3994.
(44) Demir, A. S.; Findik, H.; Saygili, N.; Subasi, N. T. Tetrahedron 2010, 66, 1308.
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