炔基环氧化合物的开环反应研究
摘要
本文主要对环氧化合物的开环反应与联烯的合成方法进行了介绍,并对酸催化炔基环氧化合物合成联烯的方法进行了研究。本文共分三章进行论述,其摘要如下：
1.环氧化合物是一种重要的含氧三元杂环化合物。它易于制备,反应活性高,是一类重要的合成原料和中间体。另外,各类亲核试剂对环氧的开环得到了区域选择性和反式的立体选择性都较高的开环产物。因此,环氧化合物被广泛应用于医药、农药、食品、日用化工等诸多有机合成领域。
2.联烯是含有1,2-丙二烯官能团的重要化合物,具有很高的反应活性。近年来,人们对联烯化合物的合成投入了极大的热情,不仅对一些经典的联烯的合成反应提出了改进或扩展了应用范围,而且提出了新颖的反应类型。利用炔基的重排来合成联烯是一种重要的方法。
3.酸催化的炔基环氧化合物合成联烯化合物的方法和表征。本文论述了一个新颖有效的构建联烯的方法,该方法包括环氧的开环,炔基进攻,羟基诱导三部分,并对联烯产物进行了表征。
In this paper, the ring-opening of epoxides, and the synthesis methods of allenes were introduced, and the methods of acid-catalyzed epoxy alkynes into allenes were researched. Expounded in this article is divided into three chapters, which are summarized as follows:
1. Epoxide and its derivatives are important triatomic heterocyclic compounds. Due to their ease of preparation and ready reactivity, epoxides are important starting materials and intermediates in organic synthesis. In addition, high reactivity with various nucleophiles leads to high regioselective and trans-stereospecific ring-opening products. Therefore, they are widely applied in medicine, pesticides, food, household chemicals and so on.
2. Allenes, which contain the functional group of 1,2-propadiene, are highly reactive. In recent years, people pay more enthusiasm to the synthesis of allene, not only to improve and extend the scope of application of some classical synthesis allene, but also put forward a novel type of reaction. Using the rearrangement of alkynyl epoxide to synthesis allene is a kind of new method.
3. Synthesis and characterization of allenes through acid-catalyed epoxy alkynes. A novel and efficient method of construction of allenes had been found, which included an epoxy-opening, alkyne-attacking, hydroxyl-inducing. The product allenes had been characterized.
1.环氧化合物是一种重要的含氧三元杂环化合物。它易于制备,反应活性高,是一类重要的合成原料和中间体。另外,各类亲核试剂对环氧的开环得到了区域选择性和反式的立体选择性都较高的开环产物。因此,环氧化合物被广泛应用于医药、农药、食品、日用化工等诸多有机合成领域。
2.联烯是含有1,2-丙二烯官能团的重要化合物,具有很高的反应活性。近年来,人们对联烯化合物的合成投入了极大的热情,不仅对一些经典的联烯的合成反应提出了改进或扩展了应用范围,而且提出了新颖的反应类型。利用炔基的重排来合成联烯是一种重要的方法。
3.酸催化的炔基环氧化合物合成联烯化合物的方法和表征。本文论述了一个新颖有效的构建联烯的方法,该方法包括环氧的开环,炔基进攻,羟基诱导三部分,并对联烯产物进行了表征。
In this paper, the ring-opening of epoxides, and the synthesis methods of allenes were introduced, and the methods of acid-catalyzed epoxy alkynes into allenes were researched. Expounded in this article is divided into three chapters, which are summarized as follows:
1. Epoxide and its derivatives are important triatomic heterocyclic compounds. Due to their ease of preparation and ready reactivity, epoxides are important starting materials and intermediates in organic synthesis. In addition, high reactivity with various nucleophiles leads to high regioselective and trans-stereospecific ring-opening products. Therefore, they are widely applied in medicine, pesticides, food, household chemicals and so on.
2. Allenes, which contain the functional group of 1,2-propadiene, are highly reactive. In recent years, people pay more enthusiasm to the synthesis of allene, not only to improve and extend the scope of application of some classical synthesis allene, but also put forward a novel type of reaction. Using the rearrangement of alkynyl epoxide to synthesis allene is a kind of new method.
3. Synthesis and characterization of allenes through acid-catalyed epoxy alkynes. A novel and efficient method of construction of allenes had been found, which included an epoxy-opening, alkyne-attacking, hydroxyl-inducing. The product allenes had been characterized.
引文
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2.李祖义；金浩；石俊.有机合成,2001,21(4),247-251.
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4. Parker, R. E. Chem. Rev.,1959,59,737-799.
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6. Bournaud, C.; Bonin, M.; Micouin, L. Org. Lett.,2006,8,3041-3943.
7. Movassaghi, M., Jacobsen, E. N.,J.Am. Chem. Soc.,2002,24,2456-2457.
8. Meyer, O.; Ponaire, S.; Rohmer, M.; Catherine, G.-B. Org. Lett.,2006,8, 4347-4350.
9. Tarselli, M. A.; Zuccarello J. L.; Lee S. J.; Gagne, M. R. Org. Lett.,2009,11, 3490-3492.
10. Dai, L.-Z.; Qi, M.-J.; Shi, Y.-L.; Liu, X.-G.; Shi, M. Org. Lett.,2007,9, 3191-3194.
11. Shu, X.-Z.; Liu, X.-Y.; Ji, K.-G.; Xiao, H.-Q.; Liang, Y.-M. Chem. Eur. J.,2008, 14,5282-5289.
12. Ji, K.-G.; Shen, Y.-W.; Shu, X.-Z.; Xiao, H.-Q.; Bian, Y.-J.; Liang, Y.-M. Adv. Synth. Catal.2008,350,1275-1280.
13.杨宏洲；顾彦龙；邓友全.有机化学,2002，22,995-998.
14. Morten, Christopher J.; Jamison, Timothy F. J. Am. Chem. Soc.,2009,131, 6678-6679.
15. Righi, G.; Bovicelli, P.; Sperandio, A. Tetrahedron,2000,56,1733-1737.
16. Schaus, S. E.; Brandes, B. D.; Larrow, J. F. J. Am. Chem. Soc.,2002,124, 1307-1315.
17.李新生；沈宗旋；张雅文.有机化学,2002，22,327-330.
1. Burton, B. S.; Pechmann, H. V Chem. Ber.1887,20,145.
2. Jones, E. R. H.; Mansfield, C. H.; Whiting, M. C. J. Chem. Soc.1954,3208.
3. Ohno, H.; Toda, A.; Oishi, S.; Tanaka, T.; Takemoto, Y.; Fujiib, N.; Ibuka, T. Tetrahedron Letters,2000,41,5131-5134.
4. Ogasawara, M.; Nagano, T.; Hayashi, T. J. Org. Chem.,2005,70,5764-5767.
5. Kolakowski, R. V.; Manpadi, M.; Zhang, Y.; Emge, T. J.; Williams, L. J. J. AM. CHEM. SOC.,2009,131,12910-12911.
6. Nakano, M.; Furuichi, N.; Mori, H.; Katsumura, S. Tetrahedron Letters,2001,42, 7307-7310.
7. Satoh, T.; Noguchi, T.; Miyagawa, T. Tetrahedron Letters,2008,49,5689-5692.
8. Satoh, T.; Sakamoto, T.; Watanabe, M. Tetrahedron Letters,2002,43,2043-2046.
9. Satoh, T.; Gouda, Y. Tetrahedron Letters,2006,47,2835-2838.
10. Node, M.; Fujiwara, T.; Ichihashi, S.; Nishide, K. Tetrahedron Letters,1998,39, 6331-6334.
11. Hara, R.; Ura, Y; Huo, S.; Kasai, K.; Suzuki, N.; Takahashi, T. Inorganica Chimica Acta,2000,300-302,741-748.
12. Peng, W.; Zhu, S. Tetrahedron,2003,59,4641-4649.
13. Fandrick, D. R.; Reeves, J. T.; Tan, Z.; Lee, H.; Song, J. J.; Yee, N. K.; Senanayake, C. H. Org. Lett.,2009,11,5458-5461.
14. Zeng, X.; Frey, G. D.; Kousar, S.; Bertrand, G. Chem. Eur. J.,2009,15, 3056-3060.
15. Ma, S.; Zhang, A. J. Org. Chem.,1998,63,9601-9604.
16. Kuang, J.; Ma, S. J. Org. Chem.,2009,74,1763-1765.
17. Varghese, J.; Zouev, I.; Aufauvre, L.; Knochel, P.; Marek, I. Eur. J. Org. Chem., 2002,4151-4158.
18. Kobayashi, K.; Naka, H.; Wheatley, A. E. H.; Kondo, Y. Org. Lett.,2008,10, 3375-3377.
19. Jose, L. G. R.; Vanesa, M.; Jose, A. Angew. Chem. Int. Ed.,2008,47,6836-6839.
20. Varghese, J.; Knochel, P.; Marek, I. Org. Lett.,2000,2,2849-2852.
21. Takahashi, T.; Hara, R.; Huo, S.; Ura, Y.; Leese, M. P.; Suzuki, N. Tetrahedron Letters,1997,38,8723-8726.
22. Wendling, F.; Miesch, M. Org. Lett.,2001,3,2689-2691.
23. Bi, H.-P.; Liu, X.-Y.; Gou, F.-R.; Guo, L.-N.; Duan, X.-H.; Liang, Y.-M. Org. Lett., 2007,9,3527-3529.
24. Ansorge, M.; Polborn, K.; Miiller, T. J. J. Journal of Organometallic Chemistry, 2001,630,198-204.
25. Franck-Neumann, M.; Martina, D.; Neff, D. Tetrahedron:Asymmetry,1998,9, 697-708.
26. Burger, A.; Roussel, J.-P.; Hetru, C.; Hoffmann, J. A.; Luu, B. Tetrahedron,1989, 45,155.
27. Li, J.; Kong, W.; Fu, C.; Ma, S. J. Org. Chem.,2009,74,5104-5106.
28. Jose, G. L.-C.; Armando, S.-G. M.; Carmen, O.-A.; Alfredo, T.; Henri, R.; Andree, P.; Cecilio, A.-T. J. Organomet. Chem.,2005,690,3664.
29. Jiang, H.; Liu, X.; Zhou, L. Chem. Eur. J.,2008,14,11305-11309.
30. Nakamura, H.; Tashiro, S.; Kamakura, T. Tetrahedron Letters,2005,46, 8333-8336.
31.毛魏魏,王三永,李春荣,杨定乔,林永成，有机化学，2007,27,784.
32. Melo, T. M. V. D. P.; Cardoso, A. L.; Gonsalves, A. M. A. R.; Storr, R. C.; Pessoa, J. C.; Paixao, J. A.; Bejab, A. M.; Silva, M. R. Tetrahedron Letters,2003,44, 6409-6412.
33. Inoue, H.; Tsubouchi, H.; Nagaoka, Y.; Tomioka, K. Tetrahedron,2003,58,83-90.
34. Zhou, H.; Liu, G.; Zeng, C. Journal of Organometallic Chemistry,2008,693, 787-791.
35. Chan, F. C. Y.; Jarman, M.; Wang, M. F.; Potter, G. A. Tetrahedron Letters,2000, 41,2447-2448.
36. Krause, N.; Hoffmann-Roder, A.; Canisius, J. Synthesis,2002,1759.
37. Ahmed, M.; Arnauld, T.; Barrett, A. G. M.; Braddock, D. C.; Flack, K.; Procopiou, P. A. Org. Lett.,2000,2,551-553.
38. Kezuka, S.; Kanemoto, K.; Takeuchia, R. Tetrahedron Letters,2004,45, 6403-6406.
39. Albano, V. G.; Bordoni, S.; Busetto, L.; Marchetti, F.; Monari, M.; Zanotti, V. Journal of Organometallic Chemistry,2003,684,37-43.
40. Matsuo, T.; Kawaguchi, H. J. AM. CHEM. SOC.,2005,127,17198-17199.
41. Kitagawa, T.; Kamada, J.; Minegishi, S.; Takeuchi, K. Org. Lett.,2000,2,3011.
42. Lewis, F. D.; Karagiannis, P. C.; Sajimon, M. C.; Lovejoy, K. S.; Zuo, X.-B.; Rubin, M.; Gevorgyan, V. Photochem. Photobiol. Sci.,2006,5,369.
1. (a) Shen, Y.-M.; Wang, B.; Shi, Y. Angew. Chem. Int. Ed. 2006,45,1429. (b) Ranu, B. C.; Jana, U. J. Org. Chem.1998,63,8212. (c) Chang, C.-L.; Kumar, M. P.; Liu, R.-S. J. Org. Chem.2004,69,2793.
2. (a) Burova, S. A.; McDonald, F. E. J. Am. Chem. Soc.2004,126,2495. (b) Kim, K.; Okamoto, S.; Sato, F. Org. Lett.2001,3,67.
3. (a) Lin, M.-Y.; Maddirala, S. J.; Liu, R.-S. Org. Lett.2005,7,1745. (b) Lin, G.-Y.; Li, C.-W.; Hung, S.-H.; Liu, R.-S. Org. Lett.2008,10,5059. (c) Dai, L.-Z.; Qi, M.-J.; Shi, Y.-L.; Liu, X.-G.; Shi, M. Org. Lett.2007,9,3191.
4. Madhushaw, R. J.; Li, C.-L.; Shen, K.-H.; Hu, C.-C.; Liu, R.-S. J. Am. Chem. Soc. 2001,123,7427.
2.李祖义；金浩；石俊.有机合成,2001,21(4),247-251.
3. Taylor, S. K. Tetrahedron,2000,56,1149-1163.
4. Parker, R. E. Chem. Rev.,1959,59,737-799.
5. Wang, L.-S.; Hollis, T. K. Org. Lett.2003,5,2543-2545.
6. Bournaud, C.; Bonin, M.; Micouin, L. Org. Lett.,2006,8,3041-3943.
7. Movassaghi, M., Jacobsen, E. N.,J.Am. Chem. Soc.,2002,24,2456-2457.
8. Meyer, O.; Ponaire, S.; Rohmer, M.; Catherine, G.-B. Org. Lett.,2006,8, 4347-4350.
9. Tarselli, M. A.; Zuccarello J. L.; Lee S. J.; Gagne, M. R. Org. Lett.,2009,11, 3490-3492.
10. Dai, L.-Z.; Qi, M.-J.; Shi, Y.-L.; Liu, X.-G.; Shi, M. Org. Lett.,2007,9, 3191-3194.
11. Shu, X.-Z.; Liu, X.-Y.; Ji, K.-G.; Xiao, H.-Q.; Liang, Y.-M. Chem. Eur. J.,2008, 14,5282-5289.
12. Ji, K.-G.; Shen, Y.-W.; Shu, X.-Z.; Xiao, H.-Q.; Bian, Y.-J.; Liang, Y.-M. Adv. Synth. Catal.2008,350,1275-1280.
13.杨宏洲；顾彦龙；邓友全.有机化学,2002，22,995-998.
14. Morten, Christopher J.; Jamison, Timothy F. J. Am. Chem. Soc.,2009,131, 6678-6679.
15. Righi, G.; Bovicelli, P.; Sperandio, A. Tetrahedron,2000,56,1733-1737.
16. Schaus, S. E.; Brandes, B. D.; Larrow, J. F. J. Am. Chem. Soc.,2002,124, 1307-1315.
17.李新生；沈宗旋；张雅文.有机化学,2002，22,327-330.
1. Burton, B. S.; Pechmann, H. V Chem. Ber.1887,20,145.
2. Jones, E. R. H.; Mansfield, C. H.; Whiting, M. C. J. Chem. Soc.1954,3208.
3. Ohno, H.; Toda, A.; Oishi, S.; Tanaka, T.; Takemoto, Y.; Fujiib, N.; Ibuka, T. Tetrahedron Letters,2000,41,5131-5134.
4. Ogasawara, M.; Nagano, T.; Hayashi, T. J. Org. Chem.,2005,70,5764-5767.
5. Kolakowski, R. V.; Manpadi, M.; Zhang, Y.; Emge, T. J.; Williams, L. J. J. AM. CHEM. SOC.,2009,131,12910-12911.
6. Nakano, M.; Furuichi, N.; Mori, H.; Katsumura, S. Tetrahedron Letters,2001,42, 7307-7310.
7. Satoh, T.; Noguchi, T.; Miyagawa, T. Tetrahedron Letters,2008,49,5689-5692.
8. Satoh, T.; Sakamoto, T.; Watanabe, M. Tetrahedron Letters,2002,43,2043-2046.
9. Satoh, T.; Gouda, Y. Tetrahedron Letters,2006,47,2835-2838.
10. Node, M.; Fujiwara, T.; Ichihashi, S.; Nishide, K. Tetrahedron Letters,1998,39, 6331-6334.
11. Hara, R.; Ura, Y; Huo, S.; Kasai, K.; Suzuki, N.; Takahashi, T. Inorganica Chimica Acta,2000,300-302,741-748.
12. Peng, W.; Zhu, S. Tetrahedron,2003,59,4641-4649.
13. Fandrick, D. R.; Reeves, J. T.; Tan, Z.; Lee, H.; Song, J. J.; Yee, N. K.; Senanayake, C. H. Org. Lett.,2009,11,5458-5461.
14. Zeng, X.; Frey, G. D.; Kousar, S.; Bertrand, G. Chem. Eur. J.,2009,15, 3056-3060.
15. Ma, S.; Zhang, A. J. Org. Chem.,1998,63,9601-9604.
16. Kuang, J.; Ma, S. J. Org. Chem.,2009,74,1763-1765.
17. Varghese, J.; Zouev, I.; Aufauvre, L.; Knochel, P.; Marek, I. Eur. J. Org. Chem., 2002,4151-4158.
18. Kobayashi, K.; Naka, H.; Wheatley, A. E. H.; Kondo, Y. Org. Lett.,2008,10, 3375-3377.
19. Jose, L. G. R.; Vanesa, M.; Jose, A. Angew. Chem. Int. Ed.,2008,47,6836-6839.
20. Varghese, J.; Knochel, P.; Marek, I. Org. Lett.,2000,2,2849-2852.
21. Takahashi, T.; Hara, R.; Huo, S.; Ura, Y.; Leese, M. P.; Suzuki, N. Tetrahedron Letters,1997,38,8723-8726.
22. Wendling, F.; Miesch, M. Org. Lett.,2001,3,2689-2691.
23. Bi, H.-P.; Liu, X.-Y.; Gou, F.-R.; Guo, L.-N.; Duan, X.-H.; Liang, Y.-M. Org. Lett., 2007,9,3527-3529.
24. Ansorge, M.; Polborn, K.; Miiller, T. J. J. Journal of Organometallic Chemistry, 2001,630,198-204.
25. Franck-Neumann, M.; Martina, D.; Neff, D. Tetrahedron:Asymmetry,1998,9, 697-708.
26. Burger, A.; Roussel, J.-P.; Hetru, C.; Hoffmann, J. A.; Luu, B. Tetrahedron,1989, 45,155.
27. Li, J.; Kong, W.; Fu, C.; Ma, S. J. Org. Chem.,2009,74,5104-5106.
28. Jose, G. L.-C.; Armando, S.-G. M.; Carmen, O.-A.; Alfredo, T.; Henri, R.; Andree, P.; Cecilio, A.-T. J. Organomet. Chem.,2005,690,3664.
29. Jiang, H.; Liu, X.; Zhou, L. Chem. Eur. J.,2008,14,11305-11309.
30. Nakamura, H.; Tashiro, S.; Kamakura, T. Tetrahedron Letters,2005,46, 8333-8336.
31.毛魏魏,王三永,李春荣,杨定乔,林永成，有机化学，2007,27,784.
32. Melo, T. M. V. D. P.; Cardoso, A. L.; Gonsalves, A. M. A. R.; Storr, R. C.; Pessoa, J. C.; Paixao, J. A.; Bejab, A. M.; Silva, M. R. Tetrahedron Letters,2003,44, 6409-6412.
33. Inoue, H.; Tsubouchi, H.; Nagaoka, Y.; Tomioka, K. Tetrahedron,2003,58,83-90.
34. Zhou, H.; Liu, G.; Zeng, C. Journal of Organometallic Chemistry,2008,693, 787-791.
35. Chan, F. C. Y.; Jarman, M.; Wang, M. F.; Potter, G. A. Tetrahedron Letters,2000, 41,2447-2448.
36. Krause, N.; Hoffmann-Roder, A.; Canisius, J. Synthesis,2002,1759.
37. Ahmed, M.; Arnauld, T.; Barrett, A. G. M.; Braddock, D. C.; Flack, K.; Procopiou, P. A. Org. Lett.,2000,2,551-553.
38. Kezuka, S.; Kanemoto, K.; Takeuchia, R. Tetrahedron Letters,2004,45, 6403-6406.
39. Albano, V. G.; Bordoni, S.; Busetto, L.; Marchetti, F.; Monari, M.; Zanotti, V. Journal of Organometallic Chemistry,2003,684,37-43.
40. Matsuo, T.; Kawaguchi, H. J. AM. CHEM. SOC.,2005,127,17198-17199.
41. Kitagawa, T.; Kamada, J.; Minegishi, S.; Takeuchi, K. Org. Lett.,2000,2,3011.
42. Lewis, F. D.; Karagiannis, P. C.; Sajimon, M. C.; Lovejoy, K. S.; Zuo, X.-B.; Rubin, M.; Gevorgyan, V. Photochem. Photobiol. Sci.,2006,5,369.
1. (a) Shen, Y.-M.; Wang, B.; Shi, Y. Angew. Chem. Int. Ed. 2006,45,1429. (b) Ranu, B. C.; Jana, U. J. Org. Chem.1998,63,8212. (c) Chang, C.-L.; Kumar, M. P.; Liu, R.-S. J. Org. Chem.2004,69,2793.
2. (a) Burova, S. A.; McDonald, F. E. J. Am. Chem. Soc.2004,126,2495. (b) Kim, K.; Okamoto, S.; Sato, F. Org. Lett.2001,3,67.
3. (a) Lin, M.-Y.; Maddirala, S. J.; Liu, R.-S. Org. Lett.2005,7,1745. (b) Lin, G.-Y.; Li, C.-W.; Hung, S.-H.; Liu, R.-S. Org. Lett.2008,10,5059. (c) Dai, L.-Z.; Qi, M.-J.; Shi, Y.-L.; Liu, X.-G.; Shi, M. Org. Lett.2007,9,3191.
4. Madhushaw, R. J.; Li, C.-L.; Shen, K.-H.; Hu, C.-C.; Liu, R.-S. J. Am. Chem. Soc. 2001,123,7427.