Please use this identifier to cite or link to this item:
標題: Preparation and characterization of several P-N bond containing secondary phosphine oxides and their ligated palladium complexes: Application of these ligands in Catellani reaction to the formation of Carbazole derivatives
作者: 陳雅倩
Ya-Qian Chen
關鍵字: Catellani reaction;C-H activation;Norbornene;Dicyclopentadiene;Indole;Palladium;Carbazole;Catellani 反應;C-H活化;壬硼烷;雙環戊二烯;吲哚;鈀;咔唑
引用: 1. Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457-2483. 2. Hartwig, J. F.; Kawatsura, M.; Hauck, S. I.; Shaughnessy, K. H.; Alcazar-Roman, L. M. J. Org. Chem. 1999, 64, 5575-5580. 3. Ittel, S. D.; Tolman, C. A.; English, A. D.; Jesson, J. P. J. Am. Chem. Soc. 1978, 100, 7577-7585. 4. Franzen, J.; Marigo, M.; Fielenbach, D.; Wabnitz, T. C.; Kjaersgaard, A.; Jorgensen, K. A. J. Am. Chem. Soc. 2005, 127, 18296-18304. 5. Yin, J. J.; Rainka, M. P.; Zhang, X. X.; Buchwald, S. L. J. Am. Chem. Soc. 2002, 124, 1162-1163. 6. 廖釗鋙; 吳耀庭. 科學發展. 2011, 462, 60-65. 7. Suzuki, A. Acc. Chem. Res. 1982, 15, 178-184. 8. Suzuki, A. J. Organomet. Chem. 1999, 576, 147-168. 9. Bedford, R. B.; Cazin, C. S. J. Chem. Commun. 2001, 1540-1541. 10. Beller, M.; Blaser, H. U., In Platinum Metals Review, 2013, 57, 272-280. 11. Heck, R. F.; Nolley, J. P. J. Org. Chem. 1972, 37, 2320-2322. 12. Cabri, W.; Candiani, I. Accounts. Chem. Res. 1995, 28, 2-7. 13. Armstrong, R. W.; Combs, A. P.; Tempest, P. A.; Brown, S. D.; Keating, T. A. Acc. Chem. Res. 1996, 29, 123-131. 14. Ogata, Y.; Kawasaki, A. J. Chem. Soc B. 1971, 325-329. 15. Ramos, L. M.; Ponce de Leon y Tobio, A. Y.; dos Santos, M. R.; de Oliveira, H. C.; Gomes, A. F.; Gozzo, F. C.; de Oliveira, A. L.; Neto, B. A. J. Org. Chem. 2012, 77, 10184-10193. 16. Xu, L. W.; Xia, C. G.; Li, L. J. Org. Chem. 2004, 69, 8482-8484. 17. Eynde, J. J. V.; Mayence, A. Molecules. 2003, 8, 381-391. 18. Catellani, M.; Chiusoli, G. P.; Peloso, C. Tetrahedron. Lett. 1983, 24, 813-816. 19. Catellani, M.; Motti, E.; Della Ca, N. Accounts. Chem. Res. 2008, 41, 1512-1522. 20. Catellani, M.; Deledda, S.; Ganchegui, B.; Henin, F.; Motti, E.; Muzart, J. J. Organomet. Chem. 2003, 687, 473-482. 21. Wilhelm, T.; Lautens, M. Org. Lett. 2005, 7, 4053-4056. 22. Catellani, M.; Motti, E.; Paterlini, L. J. Organomet. Chem. 2000, 593, 240-244. 23. Larraufie, M. H.; Maestri, G.; Beaume, A.; Derat, E.; Ollivier, C.; Fensterbank, L.; Courillon, C.; Lacote, E.; Catellani, M.; Malacria, M. Angew. Chem. Int. Edit. 2011, 50, 12253-12256. 24. Martins, A.; Mariampillai, B.; Lautens, M. Top. Curr. Chem. 2009, 292, 1-33. 25. Jiao, L.; Herdtweck, E.; Bach, T. J. Am. Chem. Soc. 2012, 134, 14563-14572. 26. Junge, K.; Wendt, B.; Westerhaus, F. A.; Spannenberg, A.; Jiao, H.; Beller, M. Chemistry. 2012, 18, 9011-9018. 27. Walker, S. D.; Barder, T. E.; Martinelli, J. R.; Buchwald, S. L. Angew. Chem. Int. Edit. 2004, 43, 1871-1876. 28. Yanagisawa, A.; Touge, T.; Arai, T. Angewandte. Chemie. 2005, 44, 1546-1548. 29. Kranenburg, M.; Vanderburgt, Y. E. M.; Kamer, P. C. J.; Vanleeuwen, P. W. N. M.; Goubitz, K.; Fraanje, J. Organometallics. 1995, 14, 3081-3089. 30. C., B.; Hamann; Hartwig, J. F. J. Am. Chem. Soc. 1998, 120, 7369-7370. 31. Miura, M. Angew. Chem. Int. Edit. 2004, 43, 2201-2203. 32. Suzuma, Y.; Yamamoto, T.; Ohta, T.; Ito, Y. Chem. Lett. 2007, 36, 470-471. 33. Hoshi, T.; Nakazawa, T.; Saitoh, I.; Mori, A.; Suzuki, T.; Sakai, J. I.; Hagiwara, H. Org. Lett. 2008, 10, 2063-2066. 34. Willams, R. H.; Hamilton, L. A. J. Am. Chem. Soc. 1952, 74, 5418-5420. 35. Li, G. Y. Angew. Chem. Int. Edit. 2001, 40, 1513-1516. 36. Ackermann, L.; Born, R. Angew. Chem. Int. Edit. 2005, 44, 2444-2447. 37. 蔡詩宏,碩士論文,中興大學化學研究所,民國九七年. 38. 鐘琳瑛,碩士論文,中興大學化學研究所,民國九八年. 39. 胡登富,碩士論文,中興大學化學研究所,民國九九年. 40. 王律為,碩士論文,中興大學化學研究所,民國一O O年. 41. 張志宏,碩士論文,中興大學化學研究所,民國一O一年. 42. 韋竹鴻,碩士論文,中興大學化學研究所,民國九五年. 43. 吳承恩,碩士論文,中興大學化學研究所,民國九五年. 44. Wei, C. H.; Wu, C. E.; Huang, Y. L.; Kultyshev, R. G.; Hong, F. E. Chem. Eur. J. 2007, 13, 1583-1593. 45. 林冠宇,碩士論文,中興大學化學研究所,民國一O一年. 46. 黃旻楷,碩士論文,中興大學化學研究所,民國一O二年. 47. Jiao, L.; Bach, T. J. Am. Chem. Soc. 2011, 133, 12990-12993. 48. Maestri, G.; Motti, E.; Della Ca, N.; Malacria, M.; Derat, E.; Catellani, M. J. Am. Chem. Soc. 2011, 133, 8574-8585. 49. Chai, D. I.; Thansandote, P.; Lautens, M. Chemistry. 2011, 17, 8175-8188. 50. Pialat, A.; Liegault, B.; Taillefer, M. Oxidative para-Triflation of Acetanilides. Org. Lett. 2013, 15, 1764-1767. 51. Ca, N. D.; Sassi, G.; Catellani, M. Adv. Synth. Catal. 2008, 350, 2179-2182.
A new type of secondary phosphine oxides (SPOs, 3a-3c) containing N-P bond have been successfully prepared. These ligands are stable toward air and moisture, and thereby are good for long time storage. The molecular structures of 3b and palladium complexes 4a, 4b were determined by single crystal X-ray diffraction methods. After screening the ligands for Catellani reaction to synthesize 1-methyl-9H-carbazole, 3b exhibited satisfactory efficiency. Furthermore, a mechanism was proposed to accomdate the process for the formation of 1-substituted carbazoles by C-C and C-N bonds cross-coupling.
The catalytic performances of these ligands on Catellani type N-H activation reactions were studied. Unfortunately, the results are not as good as expected. However, we obtained the palladium complex 2A from the crystal growing process. Since the intermediate products 3A and 5A are available, we proposed a reaction machanisim which is correlated to the formation of 2A complex. Besides, we were able to repeat the N-H activation reaction which reported by Bach and obtained the crystal structure of intermediate 1A. In addition, a series of closely related compounds 1B, 2B and 3B were obtained from similar reactions by replacing norbornene to dicyclopentadiene. It is worthy of noting that theses crystal structures are unique for palladium complexes containing norbornene or dicyclopentadiene.

本研究成功地製備出以芳香環二級胺為骨架的含氮-磷鍵之二級氧化磷基3a-3c,並利用X-ray單晶繞射法鑑定分子3b和含鈀金屬錯合物4a和4b等的結構。此類型配位基在空氣及水氣下具有高穩定性,故可長期於室溫下保存。經過優選後發現配位基3b可應用於Catellani reaction來合成1-Methyl-9H-carbazole,在短時間內即可達到不錯的產率。此外,在本研究中對於以C-C和C-N鍵形成Carbazoles的方法,提出一個更完整的反應機構。
另外,在本研究 中也嘗試將二級氧化磷基應用於Catellani型態的N-H鍵活化反應上,但是結果並不如預期。然而,卻意外地得到了鈀金屬錯合物2A的晶體,並藉由得到中間產物3A及5A,進而提出一個對應的反應機構。在本研究中也順利得到了由Bach所提出的N-H鍵活化反應之中間產物1A的晶體結構;此外,將反應中所使用的Norbornene改為具有類似結構的Dicyclopentadiene來進行反應,仍可得到類似的產物1B、2B及3B等相對應化合物及其晶體結構。此類型含有Norbornene或是Dicyclopentadiene的鈀金屬錯合物晶體結構非常獨特且鮮少被文獻報導。
Rights: 同意授權瀏覽/列印電子全文服務,2015-06-25起公開。
Appears in Collections:化學系所

Files in This Item:
File Description SizeFormat Existing users please Login
nchu-104-7102051061-1.pdf13.04 MBAdobe PDFThis file is only available in the university internal network    Request a copy
Show full item record

Google ScholarTM


Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.