Title

鈷金屬催化劑對於熊田耦合反應的催化應用

Translated Titles

Development of Cobalt Catalysts for Catalytic Kumada Couplings

Authors

唐魁謙

Key Words

熊田耦合反應 ; 鈷金屬 ; 長碳鏈間的耦合 ; 鄰位多取代 ; 室溫的條件 ; Kumada Couplings ; CoCl2-TMEDA ; Cobalt Catalysts ; N-heterocyclic carbene ; Csp3-Csp3 coupling ; tri-ortho-substituted biaryls

PublicationName

中山大學化學系研究所學位論文

Volume or Term/Year and Month of Publication

2014年

Academic Degree Category

碩士

Advisor

梁蘭昌

Content Language

繁體中文

Chinese Abstract

第一部份: 我們利用CoCl2和 TMEDA 去進行 Kumada 耦合催化反應,在一級和二級烷基鹵化物和芳基或烷基的 Grignard reagent耦合反應中在室溫條件下不需要緩慢的添加Grignard reagent,由其在長碳鏈間的耦合反應中在常溫 15 分鐘的反應條件下即可得到相當高的目標產物產率,在 primary and second alkyl halide 和 aryl 格林那試劑的偶和反應我們也可以得到極佳的催化效果,在反應機制的探討中我們利用自由基抑制劑和 radical clock substrate 去證明我們的催化反應是走一個自由基的機制,所有的偶和產物我們皆有使用NMR 去進行檢測確定在反應過程中沒生成異構化的副產物。 第二部分: 我們利用相當便宜且環境友善的 CoCl2 和 air stable NHC ligand ,去進行 aryl-aryl Kumada cross coupling 合成一系列的 biaryl compounds ,此催化系統對於 functionalized aryl 、雜環、和鄰位上具有取代基 aryl 皆有很高的活性,且在室溫的條件下即可合成出多種鄰位多取代的 biaryls.

English Abstract

Abstract 1. Cobalt(TMEDA)-Catalyzed Cross-coupling Reactions of Primary or Secondary Alkyl Halides with Alkyl and Aryl Grignard Reagents A simple and convenient catalytic system (CoCl2-TMEDA) is found to couple primary and secondary alkyl halides with alkyl and aryl Grignard reagents. The results show that the Csp3-Csp3 coupling completed in 15 mins at room temperature in the absence of β-H elimination side product, and also exhibit high reactivity between alkyl halides and aryl Grignard reagents, and show no tolerance toward sensitive functional groups. The mechanism exploration depending on the reaction of radical clock substrate suggests that the reaction proceeds via the radical path. 2. Cobalt-NHC catalyzed biaryl preparation An efficient and high-yield cross-coupling methodology of (hetero)aryl halides with aryl Grignard reagents was developed with the employment of catalytic CoCl2 and N-heterocyclic carbene (NHC) under mild conditions. This catalysis allows for the synthesis of sterically congested tri-ortho-substituted biaryls and tolerates various functional groups.

Topic Category 基礎與應用科學 > 化學
理學院 > 化學系研究所
Reference
  1. (2) Xi, Z.; Zhou, Y.; Chen, W. J. Org. Chem 2008, 73, 8497.
    連結:
  2. (3) Wang, L.; Wang, Z.-X. Org. Lett .2007, 9, 4335.
    連結:
  3. (5) Zhou, J.; Fu, G. C. J. Am. Chem. Soc.2003, 125, 12527.
    連結:
  4. (6) Li, H. J.; Wang, L. Chem. Eur. J .2006, 2006, 5099.
    連結:
  5. (9) Mee, S. P. H.; Lee, V.; Baldwin, J. E. Angew. Chem. Int. Ed .2004, 43, 1132.
    連結:
  6. (11) Molander, G. A.; Iannazzo, L. J. Org. Chem 2011, 76, 9182.
    連結:
  7. (12) Powell, D. A.; Fu, G. C. J. Am. Chem. Soc.2004, 126, 7788.
    連結:
  8. (13) Lee, J.-Y.; Fu, G. C. J. Am. Chem. Soc.2003, 125, 5616.
    連結:
  9. (14) Fors, B. P.; Buchwald, S. L. J. Am. Chem. Soc. 2010, 132, 15914.
    連結:
  10. (15) Shen, Q.; Hartwig, J. F. Org. Lett. 2008, 10, 4109.
    連結:
  11. (16) Old, D. W.; Wolfe, J. P.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 120, 9722.
    連結:
  12. (20) Chen, Y.-J.; Chen, H.-H. Org. Lett 2006, 8, 5609.
    連結:
  13. (21) Zhang, Q.; Wang, D.; Wang, X.; Ding, K. J. Org. Chem 2009, 74, 7187.
    連結:
  14. (23) Tamao, K.; Sumitani, K.; Kumada, M. J. Am. Chem. Soc. 1972, 94, 4374.
    連結:
  15. (25) Nakamura, M.; Matsuo, K.; Ito, S.; Nakamura, E. J. AM. CHEM. SOC. 2004, 126, 3686.
    連結:
  16. (26) Huang, J.; Nolan, S. P. J. Am. Chem. Soc. 1999, 121, 9889.
    連結:
  17. (27) Nakamura, M.; Hatakeyama, T. J. Am. Chem. Soc. 2007, 129, 9844.
    連結:
  18. (33) Fürstner, A.; Leitner, A.; Méndez, M.; Krause, H. J. Am. Chem. Soc. 2002, 124, 13856.
    連結:
  19. (34) Ohmiya, H.; Yorimitsu, H.; Oshima, K. J. Am. Chem. Soc. 2006, 128, 1886.
    連結:
  20. (36) Bedford, R. B.; Betham, M.; Bruce, D. W.; Danopoulos, A. A.; Frost, R. M.; Hird, M. The Journal of Organic Chemistry 2005, 71, 1104.
    連結:
  21. (37) Frisch, A. C.; Beller, M. Angew. Chem. Int. Ed. 2005, 44, 674.
    連結:
  22. (41) Terao, J.; Kambe, N. Acc. Chem. Res. 2008, 41, 1545.
    連結:
  23. (45) Vechorkin, O.; Barmaz, D.; Proust, V.; Hu, X. J. Am. Chem. Soc. 2009, 131, 12078.
    連結:
  24. (52) Li, C.; Xiao, G.; Zhao, Q.; Liu, H.; Wang, T.; Tang, W. Organic Chemistry Frontiers 2014, 1, 225.
    連結:
  25. (1) Kirchhoff, J. H.; Netherton, M. R.; Hills, I. D.; Fu, G. C. J. Am. Chem. Soc.2002, 124, 13662.
  26. (4) Hadei, N.; Kantchev, E. A. B.; O''Brie, C. J.; Organ, M. G. Org. Lett .2005, 7, 3805.
  27. (7) Xu, H.-J.; Zhao, Y.-Q.; Zhou, X.-F. J. Org. Chem 2011, 76, 8036.
  28. (8) Kantchev, E. A. B.; Peh, G.-R.; Zhang, C.; Ying, J. Y. Org. Lett .2008, 10, 3949.
  29. (10) Li, J.-H.; Liang, Y.; Wang, D.-P.; Liu, W.-J.; Xie, Y.-X.; Yin, D.-L. J. Org. Chem 2005, 70, 2832.
  30. (17) Pompeo, M.; Farmer, J. L.; Froese, R. D. J.; Organ, M. G. Angew. Chem. Int. Ed 2014, 53, 3223.
  31. (18) Organ, M. G.; Abdel-Hadi, M.; Avola, S.; Dubovyk, I.; Hadei, N.; Kantchev, E. A. B.; O''Brien, C. J.; Sayah, M.; Valente, C. Chem. Eur. J .2008, 14, 2443.
  32. (19) Kwong, F. Y.; Klapars, A.; Buchwald, S. L. Org. Lett. 2002, 4, 581.
  33. (22) Altman, R. A.; Shafir, A.; Choi, A.; Lichtor, P. A.; Buchwald, S. L. J. Org. Chem 2007, 73, 284.
  34. (24) Guisan-Ceinos, M.; Tato, F.; Bunuel, E.; Calle, P.; Cardenas, D. J. Chem. Sci. 2013, 4, 1098.
  35. (28) Knochel, P.; Dohle, W.; Gommermann, N.; Kneisel, F. F.; Kopp, F.; Korn, T.; Sapountzis, I.; Vu, V. A. Angew. Chem. Int. Ed 2003, 42, 4302.
  36. (29) Kuzmina, O. M.; Steib, A. K.; Flubacher, D.; Knochel, P. Org. Lett. 2012, 14, 4818.
  37. (30) Steib, A. K.; Kuzmina, O. M.; Fernandez, S.; Flubacher, D.; Knochel, P. J. Am. Chem. Soc. 2013, 135, 15346.
  38. (31) Liang, L.-C.; Chien, P.-S.; Lin, J.-M.; Huang, M.-H.; Huang, Y.-L.; Liao, J.-H. Organometallics 2006, 25, 1399.
  39. (32) Nakai, K.; Yoshida, Y.; Kurahashi, T.; Matsubara, S. J. Am. Chem. Soc. 2014.
  40. (35) Xia, C.-L.; Xie, C.-F.; Wu, Y.-F.; Sun, H.-M.; Shen, Q.; Zhang, Y. Org. Biomol. Chem. 2013, 11, 8135.
  41. (38) Zhang, C.; Hwang, S. Y.; Trout, A.; Peng, Z. Journal of the American Chemical Society 2014.
  42. (39) Cahiez, G.; Chaboche, C.; Jézéquel, M. Tetrahedron 2000, 56, 2733.
  43. (40) Terao, J.; Watanabe, H.; Ikumi, A.; Kuniyasu, H.; Kambe, N. J. Am. Chem. Soc. 2002, 124, 4222.
  44. (42) Jana, R.; Pathak, T. P.; Sigman, M. S. Chem. Rev. 2011, 111, 1417.
  45. (43) Iwasaki, T.; Takagawa, H.; Singh, S. P.; Kuniyasu, H.; Kambe, N. J. Am. Chem. Soc. 2013, 135, 9604.
  46. (44) Terao, J.; Naitoh, Y.; Kuniyasu, H.; Kambe, N. Chem. Commun. 2007, 825.
  47. (46) Ohmiya, H.; Wakabayashi, K.; Yorimitsu, H.; Oshima, K. Tetrahedron 2006, 62, 2207.
  48. (47) Cahiez, G.; Chaboche, C.; Duplais, C.; Giulliani, A.; Moyeux, A. Advanced Synthesis & Catalysis 2008, 350, 1484.
  49. (48) Noda, D.; Sunada, Y.; Hatakeyama, T.; Nakamura, M.; Nagashima, H. Journal of the American Chemical Society 2009, 131, 6078.
  50. (49) Yang, C.-T.; Zhang, Z.-Q.; Liang, J.; Liu, J.-H.; Lu, X.-Y.; Chen, H.-H.; Liu, L. J. Am. Chem. Soc. 2012, 134, 11124.
  51. (50) Cahiez, G.; Chaboche, C.; Duplais, C.; Moyeux, A. Org. Lett. 2008, 11, 277.
  52. (51) Bedford, R. B.; Betham, M.; Bruce, D. W.; Danopoulos, A. A.; Frost, R. M.; Hird, M. J. Org. Chem. 2005, 71, 1104.
  53. (53) Zhou, W.; Napoline, J. W.; Thomas, C. M. European Journal of Inorganic Chemistry 2011, 2011, 2029.
  54. (54) Organ, M. G.; Abdel-Hadi, M.; Avola, S.; Hadei, N.; Nasielski, J.; O''Brien, C. J.; Valente, C. Chemistry – A European Journal 2007, 13, 150.
  55. (55) Hartmann, C. E.; Nolan, S. P.; Cazin, C. S. J. Organometallics 2009, 28, 2915.
  56. (56) Iglesias, M. J.; Prieto, A.; Nicasio, M. C. Org. Lett. 2012, 14, 4318.
  57. (57) 許毓麟 「Metal Complexes of Chelating Phenolate Phosphine Ligands.」 ,國立中山化學所碩士論文,2010
  58. (58) 鄭良謙 「Diphenolate Phosphine Complex of Tantalum(V) and Anilidophosphinimine Coplexes of Aluminum」 ,國立中山化學所碩士論文,2008
  59. (59) 周冠葳 「Metal Complex Containing a Chelating Amido Phosphine or Phenolate Phosphine Ligand」 ,國立中山化學所碩士論,2006