臺灣博碩士論文加值系統

合成及鑑定取代基皆為芳香族的雙亞胺化合物 (Ar)2(C4N2H6), (3e, Ar=2,6-iPr2C6H3; 3f, Ar=2,4,6-Me3C6H2; 3g, Ar=C6H6; 3h, Ar=4-BrC6H4; 3i, Ar=4-tBuC6H4; 3j, Ar=4-OMeC6H4; 3k, Ar=2,6-Me2C6H3; 3l, Ar=2-iPrC6H4; 3m, Ar=2,4-Me2C6H3)及NPN型態之二級氧化磷基，(HASPO, (Ar)2(C4N2H6P(=O)H)), (6e, Ar=2,6-iPr2C6H3; 6f, Ar=2,4,6-Me3C6H2 )，並利用X-ray單晶繞射法確認二級氧化磷基6e之結構。化合物6e及6f皆可藉由其互變異構化的特性，轉換成具有提供電子能力之配位基。將此N-P-N類型的二級氧化磷基運用在Suzuki-Miyaura偶合反應，發現6e在芳香族溴化物與氯化物的偶合反應都有不錯的效率。
此外，由合成的N-P-N類型的二級氧化基(Ar)2(C2N2H2P(=O)H) (6a) 和鈀金屬化合物Pd(OAc)2反應，得到構形奇特的錯合物8a，且由X-ray單晶繞射法確認其結構。藉由其反應條件及分子結構進一步推測8a可能的生成機制。

Several diimines (Ar)2(C4N2H6), (3e, Ar=2,6-iPr2C6H3; 3f, Ar=2,4,6-Me3C6H2; 3g, Ar=C6H6; 3h, Ar=4-BrC6H4; 3i, Ar=4-tBuC6H4; 3j, Ar=4-OMeC6H4; 3k, Ar=2,6-Me2C6H3; 3l, Ar=2-iPrC6H4; 3m, Ar=2,4-Me2C6H3), and heteroatom-substituted secondary phosphine oxides (HASPO, (Ar)2(C4N2H6P(=O)H), (6e, Ar=2,6-iPr2C6H3; 6f, Ar=2,4,6-Me3C6H2 ), were prepared. The molecular structure of 6e was determined by single-crystal X-ray diffraction methods. The tautomeric character of compound 6e or 6f makes it an authentic electron-donating ligand as conventional phosphine. These N-P-N type SPO ligands can be applied directly to palladium-catalyzed Suzuki-Miyaura cross-coupling reactions of aryl chlorides and aryl bromides. Fair to excellent efficiencies were observed.
Besides, a close related N-P-N type of SPO (Ar)2(C2N2H2P(=O)H)(6a) was synthesized. An unusual complex 8a was obtained from the reaction of 6a with Pd(OAc)2. Crystal structure of 8a was determined by single-crystal X-ray diffraction methods. The possible route for the formation of 8a from the reaction of 6a with Pd(OAc)2 was proposed.

第一章 序論 1
第一節 運用過渡金屬進行偶合反應之簡介 2
第二節 Suzuki-Miyaura偶合反應簡介 6
第三節 反應中常見之有機配位基簡介 9
第四節 以磷化物為配位基常見問題及嘗試的解決方法 13
第五節 Secondary phosphine oxide(二級氧化磷基)簡介 15
第六節 研究方向 19
第二章 結果與討論 23
第一節 芳香族取代基之Diimines製備 24
第二節 N-Heterocyclic Bromophosphines製備 25
第三節 N-Heterocyclic Phosphine Oxides製備 26
第四節 配位基6e用於Suzuki-Miyaura偶合反應 30
第五節 二級氧化磷基(6e)、雙亞胺配位基(3i)與鈀金屬形成之鈀錯合物及其對反應可能造成之影響 44
第三章 結論 48
第四章 實驗 49
第一節 儀器與藥品 50
第二節 操作技巧 55
第三節 合成與鑑定 56
第四節 Suzuki-Miyaura偶合反應步驟 70
第五節 偶合產物光譜數據 71
參考文獻 73
附錄 77
Diimines光譜數據 78
N-Heterocyclic Phosphine Oxides 光譜數據 97
Suzuki Reaction 產物光譜圖 105
晶體數據 112
Scheme 1-1-1. 常見的偶合反應 4
Scheme 1-1-2. 過渡金屬催化偶合反應重要程序 4
Scheme 1-2-1. Suzuki-Miyaura偶合反應通式 6
Scheme 1-2-2. Suzuki-Miyaura循環催化反應機制簡單圖示 7
Scheme 1-5-1. 二級氧化磷基之互變異構及其與金屬之配位模式 16
Scheme 1-5-2. 二級氧化磷基與金屬在鹼性環境形成之錯合物 17
Scheme 1-6-1. Ackermann團隊發表的含單鍵類型之二級氧化磷基 19
Scheme 1-6-2. 本實驗室李佾璋合成的NPN類型的二級氧化磷基 20
Scheme 1-6-3. 本研究合成之NPN類型的二級氧化磷基 20
Scheme 1-6-4. 合成之雙亞胺配位基 21
Scheme 2-1-1. 芳香族取代基3e ~ 3m化合物的製備方法 24
Scheme 2-2-1. N-Heterocyclic Bromophosphines的製備 25
Scheme 2-3-1. N-Heterocyclic Phosphine Oxides 的製備 26
Scheme 2-3-2. 6a之合成反應步驟 27
Scheme 2-3-3. 錯合物8a形成之反應機構推測 29
Table 2-4-1. Effect of the base in Suzuki-Miyaura reaction 31
Table 2-4-2. Effect of the base in Suzuki-Miyaura reaction 32
Table 2-4-3. Effect of the palladium in Suzuki-Miyaura reaction 33
Table 2-4-4. Effect of the solvent in Suzuki-Miyaura reaction 34
Table 2-4-5. Effect of the Pd/6e ratio in Suzuki-Miyaura reaction 35
Table 2-4-6. Effect of the ligand in Suzuki-Miyaura reaction 36
Table 2-4-7. The reaction of various substrates under the optimum conditions 38
Table 2-4-8. Effect of the base in Suzuki-Miyaura reaction 39
Table 2-4-9. Effect of the palladium in Suzuki-Miyaura reaction 40
Table 2-4-10. Effect of the solvent in Suzuki-Miyaura reaction 41
Table 2-4-11. Effect of the Pd/6e ratio in Suzuki-Miyaura reaction 42
Table 2-4-12. The reaction of various substrates under the optimum conditions 43
Table 2-5-1. 晶體8a、6e、7e之比較 45
Table 2-5-2. 晶體3i、4i之比較 47
Figure 1-3-1. 一般單牙的三級含磷配位基 9
Figure 1-3-2. 常見磷化物的不同取代基造成的空間立障及鍵結強度 10
Figure 1-3-3. Buchwald類型之含磷配位基 10
Figure 1-3-4. Beller類型之含磷配位基 10
Figure 1-3-5. 二茂鐵為主體的含磷配位基 10
Figure 1-3-6. 碳烯為主體架構的氮異環碳烯配位基 11
Figure 1-3-7. 改變氮上的取代基之雙亞胺配位基20a 12
Figure 1-3-8. 改變NCCN骨架上的取代基之雙亞胺配位基 12
Figure 1-5-1. 氧化磷基類型 15
Figure 1-5-2. 近年來由本實驗室合成不同類型之二級氧化磷基
18
Figure 2-3-1. 6e晶體結構圖 27
Figure 2-3-2. 8a晶體結構圖 28
Figure 2-5-1. 雙亞胺配位基接上鈀金屬的晶體結構7e 44
Figure 2-5-2. 雙亞胺配位基3i 46
Figure 2-5-3. 雙亞胺水解後形成胺類接上鈀金屬之晶體4i 46

1. Le′pine, R.; Zhu, J. Org. Lett., 2005, 7, 2981–2984.
2. (a) Quasdorf, K.W.; Riener, M.; Petrova, K.V.; Garg, N.K. J. Am. Chem. Soc. 2009, 131, 17748–17749. (b) Gerg, N.K.; Caspi, D.D.; Stoltz, B.M. J. Am. Chem. Soc. 2005, 127, 5970–5978.
3. Ali, H.; Ait-Mohand, S.; Gosselin, S.; van Lier, J.E.; Guerin, B. J. Org. Chem. 2011, 76, 1887–1890.
4. Cheng, Y. J.; Yang, S. H.; Hsu, C. S. Chem. Rev. 2009, 109, 5868–5923.
5. Hayashi, Y.; Yamaguchi, S.; Cha, W.Y.; Kim, D.; Shinokubo, H. Org. Lett., 2011, 13, 2992–2995.
6. (a) Miyaura, N; Suzuki, A. Chem. Rev. 1995, 95, 2457–2483. (b) Jana, R.; Pathak, T. P.; Sigman, M. S. Chem. Rev. 2011, 111, 1417–1492.
7. Huang, J.; Nolan, S. P. J. Am. Chem. Soc. 1999, 121, 9889–9890.
8. (a) Heck, R. F.; Nolley, J. P. J. Org. Chem. 1972, 37, 2320–2322. (b) Wu, X. F.; Neumann, H.; Spannenberg, A.; Schulz, T.; Jiao, H.; Beller, M. J. Am. Chem. Soc. 2010, 132, 14596–14602.
9. Littke, A. F.; Fu, G. C.; Angew. Chem. Int. Ed. 1999, 111, 2568.
10. (a) Sonogashira, K.; Tohda, Y.; Hagihara, N.; Tetrahedron Lett. 1975, 16, 467–4470. (b) Dudnik, A. S.; Gevorgyan, V. Angew. Chem. Int. Ed. 2010, 49, 2096–2098.
11. (a) McGowan, M.A.; Henderson, J. L.; Buchwald, S. L. Org. Lett., 2012, 14, 1432–1435. (b) Harris, M. C.; Buchwald, S. L. J. Org. Chem. 2000, 65, 5327–5333. (c) Hartwig, J. F.; Kawatsura, M.; Hauck S. I.; Shaughnessy, K. H.; Alcazer-Roman, L. M. J. Org. Chem. 1999, 64, 5575–5580. (d) Hamann, B. C.; Hartwig, J. F. J. Am. Chem. Soc. 1998, 120, 7369–7370.
12. (a) Filler, M. A.; Musgrave, C. B.; Bent, S. F. J. Phys. Chem. C. 2007, 111, 1739–1746. (b) Shih, K. Y.; Fanwick, P. E.; Walton, R. A. Organometallics 1994, 13, 1235–1242. (c) Shih, K. Y.; Fanwick, P. E.; Walton, R. A. J. Am. Chem. Soc. 1993, 115, 9319–9320. (d) Ittel, S. D.; Tolman, C. A.; English, A. D.; Jesson, J. P. J. Am. Chem. Soc. 1978, 110, 7577–7585.
13. (a) Harr, M. S.; Presley, A. L.; Thorarensen, A. Synlett, 1999,10,1759–1581. (b) Zheng, N.; McWilliams, J. C.; Fleitz, F. J.; Armstrong III, J. D.; Volante, R. P. J. Org. Chem., 1998, 63, 9606–96070. (c) Baranano, D.; Hartwig, J. F. J. Am. Chem. Soc. 1995, 117, 2937–2938. (d)Takagi, K. Chem. Lett. 1987, 2221–2224.
14. http://www.ecompound.com/Reaction%20reference/reaction_index.
15. (a) Walker, S. D.; Barder, T. E.; Martinelli, J. R.; Buchwald, S. L. Angew. Chem. Int. Ed. 2004, 43, 1871 –1876. (b) Wolfe, J. P.; Singer, R. A.; Yang, B. H.; Buchwald, S. L. J. Am. Chem. Soc. 1999, 121, 9550–9561.
16. Parr, R. G.; Pearson, R. G. J. Am. Chem. Soc. 1983, 105, 7512–7516.
17. Suzuki, A. J. Organomet. Chem. 1999, 576, 147–168.
18. Colacot, T. J. Chem. Rev. 2003, 103, 3101–3118.
19. (a) Samojłowicz, C.; Bieniek, M.; Grela, K. Chem. Rev. 2009, 109, 3708–3742.(b) Altenhoff, G.; Goddard, R.; Lehmann, C.W.; Glorius, F. Angew. Chem. Int. Ed. 2003, 42, 3690 –3693. (c) Navarro, O.; Kelly, R. A.; Nolan, S. P. J. Am. Chem. Soc. 2003, 125, 16194–16195. (d) Gstottmayr, C. W. K.; Bohm, V. P. W.; Herdtweck, E.; Grosche, M.; Herrmann, W. A. Angew. Chem. Int. Ed. 2002, 41, 1363–1365.
20. (a) Grasa, G. A.; Singh, R.; Stevens, E. D.; Nolan, S. P. J. Organomet. Chem. 2003, 687, 269–279. (b) Paulovicova, A.; El-Ayaan, U.; Shibayama, K.; Morita, T.; Fukuda, Y. Eur. J. Inorg. Chem. 2001, 2641–2646.
21. Borisova, N. E.; Reshetova, M. D.; Ustynyuk, Y. A. Chem. Rev. 2007, 107, 46–79.
22. (a) Li, G. Y.; Zheng, G.; Noonan, A. F. J. Org. Chem. 2001, 66, 8677–8681. (b) Li, G. Y. Angew. Chem. Int. Ed. 2001, 40, 1513–1516. (c) Ackermann, L.; Born, R. Angew. Chem. Int. Ed. 2005, 44, 2444 –2447. (d) Ackermann, L.; Born, R.; Spatz, J. H.; Meyer, D. Angew. Chem. Int. Ed. 2005, 44, 7216 –7219.
23. Quin, L. D.; William, A. J. Ed. Practical Interpretation of P-31 NMR Spectra and Computer Assisted Structure Verification, Advanced Chemistry Development, Toronto, 2004.
24. Li, G. Y. J. Organomet. Chem. 2002, 653, 63–68.
25. Doak, G. O.; Freedman, L. D. Chem. Rev. 1961, 61, 31–44.
26. Hanhan, M. E. Appl. Organometal. Chem. 2008, 22, 270–275.
27. Wei, C. –H.; Wu, C. –E.; Hung, T. –L.; Kultyshev, R. G.; Hong, F. –E. Chem. Eur. J. 2007, 13, 1583–1593.
28. Jung, L. –Y.; Tsai, S. –H.; Hong, F. –E. Organometallics 2009, 28, 6044–6053.
29. Hu, D. –F.; Weng, C. –M.; Hong, F. –E. Organometallics 2011, 30, 1139–1147.
30. Huang, Y. –L.; Weng, C. –M.; Hong, F. –E. Chem. Eur. J. 2008, 14, 4426–4434.