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研究生: 蔡麗菁
Tsai Li Chin
論文名稱: 鈀錯合物催化丙二烯,醯氯化合物,有機錫試劑之三組成反應
Palladium-Catalyzed Three-Component Coupling Reactions of Allenes,Acid Chlorides,and Organotin Reagents
指導教授: 鄭建鴻教授
口試委員:
學位類別: 碩士
Master
系所名稱: 理學院 - 化學系
Department of Chemistry
論文出版年: 2000
畢業學年度: 88
語文別: 中文
論文頁數: 122
中文關鍵詞: 鈀金屬丙二烯醯氯化合物三組成反應
外文關鍵詞: palladium, allene, acid chloride, three-component coupling reaction
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  • 利用鈀金屬錯合物Pd(dba)2催化丙二烯(allene,R1R2C=C=CH2)、醯氯化合物(acid chloride,RCOCl)與有機錫試劑(organotin reagent,R33SnR4)的三分子耦合(three component coupling)反應,可以得到官能基多樣化的α,β-unsaturated ketone,R1R2C=C(COR)CH2R4。我們嘗試不同的反應條件,如改變反應溫度、溶劑、配位基、反應時間,期望找到最佳的反應條件。以甲苯為溶劑,反應溫度為90oC的條件下,可以得到最佳化產率。
    不同的有機錫試劑進行金屬轉移化(transmetallation)至鈀金屬的速率與難易程度各不相同。丙炔基(acetylene group)、塞吩基(thiophene group)、夫喃基(furan group)進行金屬轉移化的速率太快了,所得到的產物多為二分子耦合的產物。至於用丙烯基(allyl group)沒得到三分子耦合產物,也沒得到二分子耦合產物,推測是形成雙丙烯基鈀金屬錯合物。正丁烷基(n-butyl group)因轉移速率太慢,幾乎沒有反應發生。乙烯基(vinyl group)的轉移速率也很快,利用自動注射器慢慢地注入有機錫試劑,可以得到70%的預期產物。但是,α位置上有取代基的乙烯基(vinyl group),無法拿到預期得產物。苯基(phenyl group)與茴香基(anisole group)的轉移速率與丙烯基鈀金屬錯化物(π-allyl Pd complex)的形成速率互相配合,故能得到90%以上的高產率。

    利用不同官能基的醯氯化合物來進行反應,發現苯環上不同取代基所造成之電子雲密度的差異對本反應沒有明顯的影響。醯氯化合物的立體障礙愈大,則產率愈低。例如,苯環上有相同的取代基的醯氯化合物,對位、間位、鄰位三者的產率以鄰位最低。苯環、烯基、雜環取代基之醯氯化合物所得到的產率都很高,可能是形成的丙烯基鈀金屬錯合物(π-allyl Pd complex)較為穩定。至於以甲酸酯類(chloroformate)來進行反應,卻無法得到預期的產物。

    丙二烯上的取代基對三分子耦合的影響很大。如cyclohexylallene、cyclopentylallene的產率較高,可達85%以上;但如phenylallene及phenoxyallene的產率只有40%。取代基的擁擠程度會影響到兩種異構物的比例,擁擠程度愈大者,則E form產物的比例愈高,如t-butylallene因t-butyl group太過擁擠,只得到E form產物。


    Acyl chlorides R1COCl, allenes R2R3CCCH2 and organotin reagents Bu3SnR4 undergo three-component coupling reaction in toluene in the presence of Pd(dba)2 to give functionally substituted a, b unsaturated ketones R2R3C=C(COR1)CH2R4. Based on known palladium-allene and -allyl chemistry, we propose a mechanism to account for this palladium-catalyzed three-component coupling reactions.

    目 錄 摘要 ----------------------------------------------------------------------------------- I 表目錄 ----------------------------------------------------------------------------------- III 圖目錄 ----------------------------------------------------------------------------------- IV 第一章 緒論----------------------------------------------------------------------------- 1 第二章 鈀金屬催化丙二烯與醯氯化合物及有機錫試劑的三分子耦合反應 21 前言------------------------------------------------------------------------------ 21 結果與討論-------------------------------------------------------------------- 22 結論------------------------------------------------------------------------------- 50 第三章 實驗部份與光譜資料 53 實驗部份----------------------------------------------------------------------- 53 光譜資料----------------------------------------------------------------------- 55 參考文獻----------------------------------------------------------------------- 73

    參考文獻:
    1. (a) Crabtree, R. H. The Organometallic Chemistry of the Transition Metals; John Wiley & Sons, Inc.: New York, 1994; p 329.
    (b) Iqbal, J.; Bhatia, B.; Nayyar, N. K. Chem. Rev. 1994, 94, 519.
    (c) Luche, J. L.; Pertrier, C.; Barboza, S.; Carlos, J. Tetrahedron Lett. 1985, 26, 829.
    (d) Luche, J. L.; Pertrier, C.; Dupuy, C. Tetrahedron Lett. 1984, 25, 2463.
    2. (a) Jolly, P. Comprehensive Organometallic Chemistry, vol 8, Eds. Wilkinson, G.; Stone, F. G. A.; Abel, E. W., Pergamon Press, Oxford, 1982.
    (b) Jolly, P. W.; Wilke, G. The Organic Chemistry of Nickel, Vol I, II, Academic Press, New York, 1974, 1975
    3. (a) Maitlis, P. M., The Organic Chemistry of Palladium, Vol I, II, Academic Press, New York, 1971.
    (b) Heck, R. F., Palladium Reagents in Organic Synthesis, Academic Press, New York, 1978.
    4. (a) Colon, I.; Kelsey, D. R. J. Org. Chem. 1986, 51, 2627.
    (b) Kende, A. S.; LeibesKind, L. S.; Braitsch, D. M. Tetrahedron Lett. 1975, 3375
    (c) Zembayashi, M.; Tamao, K.; Yoshida, J.; Kumada, M. Tetrahedron Lett. 1877, 4089
    (d) Tadagi, K.; Hayama, N.; Inokawa, S. Bull. Chem. Soc. Jpn. 1980, 53, 3691
    (e) Takagi, K.; Hayama, N. Chem. Lett. 1983, 3691.
    (f) Takagi, K.; Hayama, N.; Sasaki, K. Bull. Chem. Soc. Jpn. 1984, 57, 1887.
    (g) Takagi, K.; Minura, H.; Inokawa, S. K. Bull. Chem. Soc. Jpn. 1984, 57, 3517.
    (h) Iyoda, M.; Sakaitani, M.; Miyazaki, T.; Oda, M. Chem. Lett. 1984, 2005.
    5. (a) Brunet, J. J.; Besazzi, D.; Courtois, A.; Caubere, P. J. Am. Chem. Soc. 1982, 104, 7030
    (b) Caubere, P. Angew. Chem. Int. Ed. Engl. 1983, 22, 599.
    (c) Vanderesse, R.; Brunet, J. J.; Caubere, D. J. Organomet. Chem. 1984, 264, 263
    6. (a) Donda, A. F.; Moretti, G. J. Organomet. Chem. 1966, 31, 985.
    (b) Luttinger, L. B. J. Org. Chem. 1962, 27, 1591.
    (c) Chini, P.; Santambrogio, A.; Palladino, N. J. Chem. Soc. C 1967, 830
    (d) Chini, P.; Palladino, M.; Santambrogio, A. J. Chem. Soc. C 1967, 836
    (e) Pasquale, R. J. J. Organomet. Chem. 1971, 32, 381.
    (f) Luttinger, L. B.; Colthup, E. C. J. Org. Chem. 1962, 27, 3752.
    (g) Luttinger, L. B. Chem. Ind. 1960, 1135.
    (h) Boston, J. L.; Sharp, D. W. A.; Wilkinson, G. J. Chem. Soc. 1962, 3488.
    7. (a) Onsager, O. T.; Wang, H.; Blindheim, U. Helv. Chim. Acta. 1969, 52, 187.
    (b) Onsager, O. T.; Wang, H.; Blindheim, U. Helv. Chim. Acta. 1969, 52, 215.
    (c) Onsager, O. T.; Wang, H.; Blindheim, U. Helv. Chim. Acta. 1962, 52, 230.
    (d) Chauvin, Y.; Phung, H. H.; Guichard-Louder, N.; Lefebvre, G. Bull. Soc. Chim. Fr. 1996, 3233.
    (e) Eberhardt, G. G.; Griffin, W. P. J. Catal. 1970, 16, 245.
    8. Sakakibara, M.; Takahashi, Y.; Sakai, S.; Ishii, Y. J. Chem. Soc. Chem. Commun. 1969, 396.
    9. Moberg, C. Tetrahedron Lett. 1981, 22, 4827.
    10. (a) Sonogashira, K.; Tohda, Y.; Hagihara, N. Tetrahedron Lett. 1975, 4467.
    (b) Tahahashi, S.; Kuroyama, T.; Sonogashira, K.; Hagihara, N. Synthesis 1986, 627.
    (c) Robius, M. J.; Barr, P. J. Tetrahedron Lett. 1981, 22, 421.
    (d) Kasahara, A.; Izami, T.; Maemura, M. Bull. Chem. Soc. Jpn. 1977, 50, 1021.
    11. Lukes, J. H.; Blom, J. E. J. Organomet. Chem. 1971, 26, C25.
    12. Dieck, H. A.; Heck, R. F. J. Am. Che. Soc. 1974, 96, 1133.
    13. (a) Rotle, G. D.; Fuller, C. E. J. Org. Chem. 1991, 56, 3493.
    (b) Badone, D.; Cecchi, R.; Guzzi, U. J. Org. Chem. 1992, 57, 6321.
    (c) Balas, L.; Jousseaume, B.; Shin, H.; Verlhac, J. B.; Willian, F. Organometallic 1991, 10, 366.
    (d) Hinkle, R. J.; Pouter, G. T.; Staug, P. J. J. Am. Chem. Soc. 1993, 115, 11626
    14. Hirota, K.; Kitade, Y.; Isobe, Y.; Maki, Y. Heterocycles 1987, 26, 355.
    15. Zhang, Y.; Wu, G.; Agnel, G.; Negishi, E.-I. J. Am. Chem. Soc. 1990, 112, 8590.
    16. Farr, R. N.; Outten, R. A.; Chen, J. C-Y.; Daves, Jr.; G. D. Organometallics 1990, 9, 3151.
    17. Heck, R. F. Acc. Chem. Res. 1979, 12, 146.
    18. Larock, R. C.; Babu, S. Tetrahedron Lett. 1987, 28, 5291.
    19. (a) Crisp, G. T.; Scatt, W. J.;Stille, J. K. J. Am. Chem. Soc. 1984, 106, 6417.
    (b) Stille, J. K.; Su, H.; Hill, D. H.; Schneider, O.; Tanaka, M.; Morrison, D. L.; Hegedus, L. S. Organometallic 1991, 10, 1993.
    20. Fugami, K.; Ohnuma, S-Y.; Kameyama, M.; Saotome, T.; Kosugi, M.; Synlett. 1999, 1, 63.
    21. Kalinin, V. N. Synthesis 1992, 413.
    22. (a) Negishi, E-I Pure Appl. Chem. 1981,53, 2333.
    (b) Vineent, P.; Beaucourt, J. P.; Pichat, L. Tetrahedron Lett. 1982, 23, 63.
    (c) Okukado, N.; Van Horn, D. E.; Klima, D. L.; Negishi, E-I. Tetrahedron Lett. 1978, 1027.
    (d) Negishi, E-I, Acc. Chem. Res. 1982, 15, 340.
    23. (a) Kobayashi, M.; negishi, E-I J. Org. Chem. 1980, 45, 5223.
    (b) Negishi, E-I.; Owczarczyk, Z. Tetrahedron Lett. 1991, 32, 6683.
    (c) Russel, C. E.; Hegedus, l. S. J. Am. Chem. Soc. 1983, 105, 943.
    (d) Erdik, E. Tetrahedron Lett. 1992, 48, 9577.
    24. (a) Stille, J. K. Pure Appl. Chem. 1985, 57, 1771.
    (b) Stille, J. K. Angew. Chem. Int. Ed. Engl. 1986, 25, 508.
    (c) Stille, J. K.; Simpson, J. H. J. Am. Chem. Soc. 1987, 109, 2138.
    (d) Stille, J. K.; Groh, B L. J. Am. Chem. Soc. 1987, 109, 813.
    (e) Evans, D. A.; Black, W. C. J. Am. Chem. Soc. 1992, 114, 2260.
    (f) Kalivretenos, A.; Stille, J. K.; hegedus, L. S. J. Org. Chem. 1991, 56, 2883.
    25. (a) Suzuki, A. Pure Appl. Chem. 1985, 57, 1747.
    (b) Miyaura, n.; Ishiyama, T.; Sasaki, H.; Ishikawa, M.; Satoh, M.; Suzuki, A. J. Am. Chem. Soc. 1989, 111, 314.
    (c) Suzuki, A. Pure Appl. Chem. 1991, 63, 419.
    (d) Ishiyama, T.; Abe, S.; Miyaura, N.; Suzuki, A. Chem. Lett. 1992, 691.
    (e) Oh-e, T.; Miyaura, N.; Suzuki, A. J. Org. Chem. 1993, 58, 2201.
    (f) Maddaford, S. P.; Keay, B. A. J. Org. Chem. 1994, 59, 6501.
    26. Negishi, E-I. Acc, Chem. Res. 1982, 15, 340.
    27. (a) Magnus, P.; Annoura, H.; Harling, J. J. Org. Chem. 1990, 55, 1709.
    (b) Yang, Z-Y.; Buoton, D. B. Tetrahedron Lett. 1990, 31, 1369.
    (c) Torneiro, H.; Tall, Y.; Castedo, L.; Mourino, A. Tetrahedron Lett. 1992, 33, 105.
    (d) Lee, A. S.; Norman, A. W.; Okamura, W. H. J. Org. Chem. 1992, 57, 3846.
    (e) Roth, G. P.; Thomas, J. A. Tetrahedron Lett. 1992, 33, 1959.
    28. Alves, T.; deOliveira, A. B.; Sniekus, V. Tetrahedron Lett. 1987, 28, 5093.
    29. Hayashi, T.; Konishi, M.; Fukushima, M.; Mise, T.; Kagotani, M.; Tajika, M.; Kumada, M. J. Am. Chem. Soc. 1982, 104, 180.
    30. Yi, C. S.; Liu, N., Organometallic 1998, 17, 3158.
    31. (a) Labadie, J. W.; Teuting, D.; Stille, J. K. J. Org. Chem. 1983, 48, 4634
    (b) Labadie, J. W.; Stille, J. K. J. Am. Chem. Soc. 1983, 109, 669
    32. Stille, J. K.; Groh, B. L. J. Am. Chem. Soc. 1987, 109, 813.
    33. Li, J.; Jiang, H.; Feng, A.; Jia, L., J. Org. Chem. 1999, 64, 5984.
    34. Ikeda, S.-I.; Cui, D.-M.; Sato, Y., J. Org. Chem. 1994, 59, 6877.
    35. Xiao, W.-J.; Alper, H.; J. Org. Chem. 1998, 63, 7939.
    36. Ishiyama, T.; Kizaki, H.; Hayashi, T.; Suzuki, A.; Miyaura, N., J. Org. Chem. 1998, 63, 4726.
    37. Zhang, Y.; Wu, G. Z.; Angel, G.; Negishi, E. I. J. Am. Chem. Soc. 1990, 112, 8590.
    38. Larock, R. C.; Gong, W. H. J. Org. Chem. 1990, 55, 407.
    39. (a) Larock, R. C.; Lee, N. H. J. Am. Chem. Soc. 1991, 113, 7815.
    (b) Larock, R. C.; Kondo, F.; Narayanan, K.; Sydes, L.; Hsu, M. H. Tetrahedron Lett. 1989, 30, 5737.
    (c) Torii, S.; Okumoto, H.; Akahoshi, F.; Kotani, T. J. Am. Chem. Soc. 1989, 111, 8932.
    40. Abelman, M. M.; Overman, L. E. J. Am. Chem. Soc. 1988, 110, 2328.
    41. Trost, B. M.; Dumas, J. Tetrahedron Lett. 1993, 34, 19.
    42. Grigg, R.; Brown, S.; Sridharan, V.; Micheal, D. U. Tetrahedron Lett. 1997, 38, 5031.
    43. Tsuji, J.; Shimizu, I.; Sugiura, T. J. Org. Chem,. 1985, 50, 537.
    44. Yamamoto, Y.; Al-Masum, M. SYNLETT 1995, 969.
    45. (a) Yamamoto, Y.; Al-Masum, M.; Asao, N. J. Am. Chem. Soc. 1994, 116, 6019.
    (b) Cazes, B.; Besson, L.; Gore, J. Tetrahedron Lett. 1995, 36, 3853.
    46. Yamamoto, Y.; Al-Masum, H.; Fujiwara, N.; Asao, N. Tetrahedron Lett. 1995, 36, 2811.
    47. Cazes, B.; Besson, L.; Gore, J. Tetrahedron Lett. 1995, 36, 3857.
    48. Yamamoto, Y.; Al-Masum, M. SYNLETT 1995, 969.
    49. Yamamoto, Y.; Al-Masum, M.; Fujiwara, N. Chem. Commun. 1996, 381.
    50. (a) Cazes, B.; Ahmar, M.; Gore, J. Tetrahedron Lett. 1985, 26, 3795.
    (b) Cazes, B.; Gore. J.; Colovray, V. Tetrahedron Lett. 1988, 29, 627.
    (c) Cazes. B.; Gore, J.; Ahmar, M. Tetrahedron Lett. 1984, 25, 4505.
    (d) Cazes, B.; Gore, J.; Kopola, N.; Friess, B. Tetrahedron Lett. 1989, 30, 3963.
    (e) Barieux, J-J.; Cazes, B.; Gore, J.; Ahmar, M. Tetrahedron Lett. 1987, 43, 513.
    51. Cazes, B.; Gauthier, V.; Gore, J. Tetrahedron Lett. 1991, 32, 915.
    52. Tsuji, J.; Shimizu, I. Chem. Lett. 1984, 233.
    53. Cazes, B.; Gore, J.; Chaptal, N.; Colvray-Gottelaned, V.; Grandjean, C. Tetrahedron Lett. 1991, 32, 1795.
    54. Cazes, B.; Gore, J.; Friess, B. Tetrahedron Lett 1988, 29, 4089.
    55. Trost, B. M.; Kottirsch, G. J. Am. Chem. Soc. 1990, 112, 2816.
    56. Yamaguchi, M.; Omata, K.; Hirama, M. Tetrahedron Lett. 1994, 35, 5689.
    57. (a) Grigg, R.; Sridharan, V.; Brown, S.; Clarkson, S. J. Chem. Soc, Chem. Commun. 1995, 1135.
    (b) Larock, R. C.; Stinn, D. E. Tetrahedron Lett. 1988, 29, 4687.
    (c) Larock, R. C.; Zenner, J. M. J. Org. Chem. 1995, 60, 482.
    (d) Larock, R. C.; Berries-Pena, N. G.; Fried, C. A. J. Org. Chem. 1991, 56, 2615.
    (e) Negishi, E.; Ma, S. J. Am. Chem. Soc, 1995, 117, 6345.
    58. Grigg, R.; Sridharan, V.; Xu, L-H. J. Chem. Soc. Chem. Commun. 1995, 1903.
    59. Cazes, B.; Gore, J-I.; Besson, L.; Bazom, J. Tetrahedron Lett. 1994,35, 2881
    60. Gallagher, T.; Scopes, D. T. C.; Davies, I. Synlett. 1993, 85.
    61. Walkup, R. D.; Guan. L.; Mosher, M. D.; Kim, S-W.; Kim, Y-S. Synlett. 1993, 88.
    62. Murai, S.; Amishiro, N. J. Am. Chem. Soc. 1991, 113, 7778.
    63. Ikeda, S. Sato, Y. J. Org. Chem. 1994, 59, 6877.
    64. Ikeda, S. Sato, Organometallics. 1999, 14, 5015.
    65. Trost, B. M. J. Am. Chem. Soc. 1999, 121, 1988.
    66. Ryu, I.; Sonoda, N. J. Am. Chem. Soc. 1991, 113, 8558.
    67. Wu, M. Y.; Yang, F. Y.; Cheng, C. H. J. Org. Chem. 1999, 64, 2471.
    68. Yang, F. Y.; Wu, M. Y.; Cheng, C. H. Tetrahedron Lett. 1999, 60, 6055.
    69. Yang, F. Y.; Wu, M. Y.; Cheng, C. H. J. Am. Chem. Soc.2000, in press.
    70. (a) Shimizu, I.; Tsuji, J. Chem. Lett. 1984, 11, 233.
    (b) Tsuji, J. Organic Synthesis with Palladium Compounds; Springer Verlag: New York, 1980
    (c) Hegedus, L. S. Transition Metals in the Synthesis of Complex Organic Molecules; University Science Books: Mill Valley, CA ,1994; Chapter 9.
    71. Suzuki, A.; Miyaura, N. Chem. Rev. 1995, 95, 2457-2483.

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