新型偶氮、胆甾及芳杂环类分子裂缝的设计、微波合成与分子识别性能研究
|
摘要
人工分子识别研究是生物有机化学前沿富有挑战性的领域之一。本文致力于新型手性与非手性偶氮酰胺类主体的设计与合成、单手性臂脱氧胆酸甲酯类碗形主体的设计与微波合成、芳杂环分子钳的设计与微波固相合成及其对中性分子和手性分子的识别与对映选择性识别性能研究，取得了一系列具有重要学术意义与应用前景的创新性成果。
设计合成了偶氮、胆甾、芳杂环三个大类四个系列共23个主体，其中手性偶氮类主体为首次设计与合成。深入研究了它们的合成方法，实现了多种简便有效的选择性合成，特别是在芳杂环分子钳的合成中，成功地采用微波固相反应，缩短了反应步骤，提高了产率，实现了一种对环境友好的，具有绿色化学意义的人工主体的合成新方法。所合成的主体具有不同的裂穴大小、不同识别位点、不同刚柔度以及不同的手性中心，其结构经IR、~1HNMR、MS、和元素分析所确证。
利用紫外光谱滴定法研究了主体分子在CHCl_3或CH_3CN中对中性分子、手性分子的识别性能，测定了配合常数及自由能变化，并利用核磁(?)及计算机模拟等手段对识别现象进行进一步解析。结果表明，大多数主体与所考察的客体分子形成了1：1型的超分子配合物。偶氮类主体对对硝基苯胺有较好的识别选择性，结合常数达5000M~(-1)左右，单手性臂胆甾主体对D-氨基酸甲酯的识别优于L-氨基酸甲酯，选择性K_D／K_L最高达89。识别的推动力主要源于主客体之间的氢键、π-πstacking、van der Waals作用等非共价键力。同时，主体的刚柔度、手臂结构不同所造成的微环境效应、主客体在大小、形状及几何空间上的互补和匹配在识别和对映选择性过程中也起重要作用。
The study on molecular recognition of artificial receptors is one of the frontiers in bioorganic chemistry. In this dissertation, the efforts were focused on design and synthesis of new types of chiral and achiral azoamide hosts,bowl-shaped steroid cholic acid methyl esters with one chiral arm under microwave irradiation and heteroaromatic molecular tweezers under microwave irradiation in solid state and their molecular recognition as well as enantioselective recognition. A series of useful and creative results have been obtained.
Three new typical molecular clefts containing azo, heteroaromatic and cholest unit have been designed and synthesized. Among them the chiral azoamide hosts were designed and synthesized for the first time. The synthetic methods of the target compounds have been systematically investigated. A series of convenient and efficient reactions have been developed. Especially, during the preparation of heteroaromatic molecular clefts, we used microwave irradiation in solid state so that steps were shortened and yields were enhanced, and a new ecofrindly synthesis method was realized. All these cleft-type receptors possess different size of clefts, different recognition sites, different rigidity and flexibility and different chiral centers. Their structures were confirmed by IR, 'HNMR, MS and element analyses.
Molecular recognition properties of the molecular clefts synthesized for neutral molecules and chiral molecules were examined by UV-visible spectra titration. The association constants (IgKa) and Gibbs free energy changes (- A GO) were determined. The 1HNMR spectra and computer-aided molecular modeling were used to elucidate further the recognition abilities. The results show that 1 : 1 inclusion complexes are formed for the most of molecular clefts with guests examined. The chiral molecular tweezers containing azo unit show excellent selective recognition ability for
p-nitroaniline, and the association constants can attend to 5000 M-1. The steroid cholic acid methyl ester molecular clefts with one chiral arm are favorable for complexation with D-amino acid methyl esters. The enantioselectivities KD/KL of some hosts are more than 89. The drive forces of molecular recognition mainly come from non-covalent forces between host and guest , such as hydrogen bond , stacking, van der Waals interaction etc. At the same time, the rigidity and flexibility of receptors, micro-environmental effects of different cleft structures, the size/shape-matching relationship between host and guest also play crucial roles in the selective molecular binding process of molecular cleft.
设计合成了偶氮、胆甾、芳杂环三个大类四个系列共23个主体，其中手性偶氮类主体为首次设计与合成。深入研究了它们的合成方法，实现了多种简便有效的选择性合成，特别是在芳杂环分子钳的合成中，成功地采用微波固相反应，缩短了反应步骤，提高了产率，实现了一种对环境友好的，具有绿色化学意义的人工主体的合成新方法。所合成的主体具有不同的裂穴大小、不同识别位点、不同刚柔度以及不同的手性中心，其结构经IR、~1HNMR、MS、和元素分析所确证。
利用紫外光谱滴定法研究了主体分子在CHCl_3或CH_3CN中对中性分子、手性分子的识别性能，测定了配合常数及自由能变化，并利用核磁(?)及计算机模拟等手段对识别现象进行进一步解析。结果表明，大多数主体与所考察的客体分子形成了1：1型的超分子配合物。偶氮类主体对对硝基苯胺有较好的识别选择性，结合常数达5000M~(-1)左右，单手性臂胆甾主体对D-氨基酸甲酯的识别优于L-氨基酸甲酯，选择性K_D／K_L最高达89。识别的推动力主要源于主客体之间的氢键、π-πstacking、van der Waals作用等非共价键力。同时，主体的刚柔度、手臂结构不同所造成的微环境效应、主客体在大小、形状及几何空间上的互补和匹配在识别和对映选择性过程中也起重要作用。
The study on molecular recognition of artificial receptors is one of the frontiers in bioorganic chemistry. In this dissertation, the efforts were focused on design and synthesis of new types of chiral and achiral azoamide hosts,bowl-shaped steroid cholic acid methyl esters with one chiral arm under microwave irradiation and heteroaromatic molecular tweezers under microwave irradiation in solid state and their molecular recognition as well as enantioselective recognition. A series of useful and creative results have been obtained.
Three new typical molecular clefts containing azo, heteroaromatic and cholest unit have been designed and synthesized. Among them the chiral azoamide hosts were designed and synthesized for the first time. The synthetic methods of the target compounds have been systematically investigated. A series of convenient and efficient reactions have been developed. Especially, during the preparation of heteroaromatic molecular clefts, we used microwave irradiation in solid state so that steps were shortened and yields were enhanced, and a new ecofrindly synthesis method was realized. All these cleft-type receptors possess different size of clefts, different recognition sites, different rigidity and flexibility and different chiral centers. Their structures were confirmed by IR, 'HNMR, MS and element analyses.
Molecular recognition properties of the molecular clefts synthesized for neutral molecules and chiral molecules were examined by UV-visible spectra titration. The association constants (IgKa) and Gibbs free energy changes (- A GO) were determined. The 1HNMR spectra and computer-aided molecular modeling were used to elucidate further the recognition abilities. The results show that 1 : 1 inclusion complexes are formed for the most of molecular clefts with guests examined. The chiral molecular tweezers containing azo unit show excellent selective recognition ability for
p-nitroaniline, and the association constants can attend to 5000 M-1. The steroid cholic acid methyl ester molecular clefts with one chiral arm are favorable for complexation with D-amino acid methyl esters. The enantioselectivities KD/KL of some hosts are more than 89. The drive forces of molecular recognition mainly come from non-covalent forces between host and guest , such as hydrogen bond , stacking, van der Waals interaction etc. At the same time, the rigidity and flexibility of receptors, micro-environmental effects of different cleft structures, the size/shape-matching relationship between host and guest also play crucial roles in the selective molecular binding process of molecular cleft.
引文
1. (a)Tabushi, I. et al. J. Am. Chem. Soc., 1985, 107, 4192
(b)Aoyama et al. Tetrahedron Lett. 1988, 29, 5271
(c)Ogoshi, H. et al. J. Syn. Org. Chem, Japan. 1989, 47, 514
(d)Aoyama et al. J. Am. Chem. Soc. 1991, 113, 6233
(e)Hayashi, T. et al. J. Am. Chem. Soc. 1993, 115, 2094
(f)Hayashi, T. et al. J. Am. Chem. Soc. 1995, 117, 11606
2. J. M. Lehn, Angew. Chem. Ed. Engl, 1990, 29, 1304.
3. Dugas, H. "Bioorganic Chemistry Frontiers" Vol.2, Springer-Verlay Berlin Heidelbery, 1991, P33, 117
4. Massahiro, I.; Takahiro, S.; Masahisa N. J. Am. Chem Soc. 2003, 125, 1140.
5. Anil, N.; Satish, A.; Umesh, G. Bull. Chem. Soc. Jpn., 2002, 75, 2161-2167.
6. Gyungse P.; John, T. T.; Tomlinson, Matt, S. M. Organic Letters, 2003, 2, 113.
7. Prasanna, S. A.; Mcelenaghan, N. D. Chem. Eur. J. 2002, 8(21), 4935-4945.
8. Rebek, J. Jr.; Askew, B.; Killoran, M.; Nerneth, D.; Lin, F. F. J. Am Chem, Soc 1987,109,2426
9． 陈淑华，罗光荣 《生物有机化学》(四川大学出版社)，1991，318．
10. Marchend, A. P. et al. Tetrahedron 1996, 52(27), 8979.
11. Yamamoto, K.; Yurnioka, H.; Okamoto, Y.; Chikamatsu, H. J. Chem. Soc. Chem. Commun 1987, 168～169
12. Habata, Y.; Bradshaw J. S.; Zhang, X. X.; izatt, R. M. J. Am. Chem. Soc. 1997, 119, 7145～7146
13. (a)Kobuke, Y.; Sumida, Y.; Hayashi, M.; Ogoshi, H. Angew. Chem. Int. Ed. Engl. 1991, 30, 1496
(b)Kobuke, Y.; Satoh, Y. K. J. Am. Chem. Soc, 1992, 114, 789.
(c)Kobuke, Y.; Kobubo, K.; Mumnakata, M. J. Am. Chem. Soc 1995, 117, 12751.
14. (a) Nabeshima, T.: Inaba, T.; Furukawa, N. Tetrahedron Lett, 1987, 28, 6211
(b) Nabeshima, T.: Inaba, T.; Furukawa, N. Hosoya, T.; Yano, Y. Inorg. Chem. 1993, 33, 1407
15. Jones, R.D.; Summerville, D. A.; Basolo. F Chem, Rev. 1979, 79, 139
16． 曹国英，奚祖威 分子催化，1994，8(3)，232
17. (a)Agarwal, D. D.; Bhatnagar, R. E; Jain, R.; Srivastava, S. J. Mol Catal. 1990, 59, 385
(b)Koola, J.D.; Kochi, J. K. Inorg. Chem. 1987, 26, 908
(C)Chatterjee, D.; Bajaj, H. C. et al. J. Mol Catal. 1993, 84, L1-L5
(d)Yoon. H.; Wagler, T. R.; O'Conner, K. J.; Burrows, C. J. J. Am. Chem. Soc 1990, 112, 4568.
18. Liu, J. G.; Xie, F. X.; Zhamg, C. Y.; Tian, Y. E; Ni, S. S. Chinese Chemical Letters 1998, 9(3) 245.
19. Seiji S.; Takahiro N.; Toshiyuki O. J. Am. Chem. Soc. 1981, 103, 111.
20. Akiyo Y.; Takashi H.; Ayako K. Bull. Chem. Soc. Jpn. 2002, 75, 1527.
21. James D C.; Andrew, J. G.; Bosnich B. Chem. Commun. 2003, 392-393.
22. Kyu-Sung J.; Kwang H. S.; Soong-Hyun K. Chemistry Letters, 2002, 1166.
23. Gale, P. A.; Coord. Chem. Rev. 2000, 199, 181.
24. Antonisse, M. M. G.; Reinhoudt, D. N. Chem. Commun. 1998, 443
25 Iao, J-H.; Chen, C-T.; Fang, J-M. Org.. Lett. 2002, 4, 561.
26 (?)en, W. E.; Causey, C. P. J. Org. Chem. 2002, 67, 5963.
27 Kondo, S.; Sakuno, Y.; Yokoyama, T.; Yano, Y. Chem. Lett. 2001, 830.
28 Prohens, R.; Tomàs, S.; Morey, J.; Deyà, P. M.; Balsester, P.; Costa, A. Tetrahedron Lett. 1998, 39, 1063.
29 Tobe, Y.; Sasaki, S.; Mizuno, M.; Hirose, K.; Naemura, K. J. Org. Chem. 1998, 63, 7481.
30 Gunnlaugsson, T.; Davis, A. P.; O'Brien, J. E.; Glynn, M. Org. Lett. 2002, 4, 2449.
31 Lee, D. H.; Lee, H. Y.; Lee, K. H.; Hong, J. I. Chem. Commun. 2001, 1188.
32 Fan, E.; Van Arman, S. A.; Kincaid, S.; Hamilton, A. D. J. Am. Chem. Soc. 1993, 115, 369.
33 Nishizawa, S.; Buhlmann, P.; Zwao, M.; Umezawa, Y.Tetrahedron Lett. 1995, 36, 6483.
34 Büohmann, P.; Nishizawa, S.; Xiao, K. P.; Umezawa, Y. Tetrahedron. 1997, 53, 1647.
35 Xiao, K. P.; Büohmann, P.; Nishizawa, S.; Amemiya, S.; Umezawa, Y. Anal. Chem. 1997, 69, 1038.
36 Kelly, T. R.; Kim, M. H. J. Am. Chem. Soc. 1994, 116, 7072.
37 Jeong, K.; Park, J. W.; Cho, Y. L. Tetrahedron Lett. 1996, 37, 2795.
38 Hamann, B. C.; Branda, N. R..; Rebek Jr, J. Tetrahedron Lett. 1993, 34, 6837.
39 Benito, J. M.; Gómez-Garci a, M.; Jiménez Blanco, J. L. J. Org. Chem. 2001, 66, 1366.
40 Corey, P. C.; William, E. A. J. Org. Chem. 2002, 67, 5963.
41 Hyejae, I.; Sunggoo, Y.; Heon, G. K. Organic Letters, 2002, 4 (17), 2897.
42 Hidekazu, M.; Simon, R.. C.; Ivan, P. Chem. Commun, 2003, 64.
43 Maria, A.; Mercedes, C. C.; Peter, T. J. Org. Chem. 2003, 68, 1097.
44 Bell, T. W.; Hou, Z.; Luo, Y.; Drew, M. G, B.; Chapoteau, E.; Czech, B. P.; Kumar, A. Science (Washington, D. C.). 1995, 269, 671.
45 Craw, J. S.; Cooper, M. D.; Hillier, I. H. J. Chem. Soc., Perkin Trans. 2. 1997, 869.
46 陈淑华，罗光荣 《生物有机化学》(四川大学出版社)，1991，211．
47 Beatriz, B.; Adrian, G. B.; Perla, B. Chem. Eur. J. 2002, 8 (13), 2931.
48 (a)薛翠花，牟其明，李玲，陈淑华．四川大学学报(自然科学版)．2001，38，124．
(b)薛翠花，胡蓉，牟其明，李方，陈淑华．化学学报．2000，58，717．
(c)薛翠花，牟其明，陈淑华．化学学报．2002，60，355．
49 Ming-Hua, X.; Jing, L.; Lin, P. J. Am. Chem. Soc. 2002, 124, 14239.
50 Helma, W.; Matthis C. N.; Matteo, M. C. Chem. Eur. J. 2003, 9(2), 442.
51 Susumu, A.; Michael, L. B.; Chan, S. O. Organic Letters, 2002, 4(24), 4249.
52 Wilen, S. H. Topics in stereochemistry, 1971, 6, 107, New York: John Wiley.
53 Prasad, E N.; Williams, D. J. Intruduction to Nonlinear Optical Effects in Molecules and Polymer, Wiley, New York, 1990.
54 Bhattacharya, S.; Dastidar, P.; Guru, T. N. Chem. Mater., 1994, 6, 531.
55 Tomori, H.; Yoshihara, H.; Ogura, K. Bull. Chem. Soc. Jpn, 1996, 69, 3581.
56 Gedye, R.; Smith, E; Westaway, K. Tetrahedron Lett, 1986, 27(3), 279
57 Gedye, R.; Smith, E; Westaway, K. Can. J Chem. 1958, 66, 17.
58 Bose, A.; Manhas, M.; Gosh, M.; Shah, M.; J. Org. Chem. 1991, 56, 6968
59 Mingos, D. M. P.; Baghurst. D. R. Chem. Soc. Rev. 1991, 20, 1.
60 Galema, S. A. Chem. Soc. Rev. 1997, 26, 233.
61 Chen, S. A.; Tseng, P. H.; Yu, H. M. J. Chin. Chem. Soc. 1997, 44, 169.
62 Dittmer, D. C. Chem. & Industry, 1997, 6 Oct., 779
63 Fan, X. J.; You, J. M.; Tan, G. Z. Progress in Chem. 1998, 10(3), 285.
64 Loupy, A. Topics in Current Chem. 1999, 206, 153.
65 金钦汉；戴树珊；黄卡玛．微波化学(科学出版社)，1999，118．
66 沙耀武；王宇；葛俊．有机化学．2001，21(2)102
67 Abdelkrim, Ben, Allonm; J. Chem. Soc., Chem. Commun. 1987, (7), 386
68 王静；姜凤超 有机化学 2002，22 (3) 212
69 彭游 赖会国 陈淑华等 四川大学学报(自然科学版)2003，40(1)，117．
70 Patil, M. L.; Jnaneshwara, G. K.; Sabde, D. P. Tetrahedron Lett. 1997, 38, 2137.
71 Anil S. G.; Dhananjay P. S.; Murlidhar S. S. Syn. Commun. 2002, 32(10), 1549.
72 Kumar, H. M.; Reddy, B. V.; Reddy, E. J. Tetrahedron Lett. 1999, 40, 2401.
73 Mane, A. S.; Chavan, V. P.; Karale, b. k. Syn. Commun. 2002, 32(17), 2633.
74 Louerat, E; Bougrin, J.; Loupy, A. Heterocycles 1998, 48(1), 234
75 彭游 牟其明 陈淑华等 第四届中国微波化学研讨会论文集 2002，140．
76 Gutierrez, E.; Loupy, A.; Bram, G. Tetrahedron Lett. 1989, 30, 945.
77 Oghaddam, E M.; Ghaffarzadeh, M.; J. Chem. Res., Synop. 1999, 9, 574.
78 Handrakala, M.; Murthy, K.V.V.S.B.S.R.; Kulkani,S.J.J. Chem. 2000, 39, 71.
79 Lingaiah N.; Narender, R.; Dattatray, A. Syn. Commun. 2002, 32(14), 2195.
80 Majid, M.; Dariush, A.; Bagher, M. Syn. Commun. 2002, 32(21), 3325.
81 S.Ravi Kanth, G.Venkat Reddy, V.V.V.N.S. Rama Rao. Syn. Commun. 2002, 32(18), 2849.
82 Das, B.; Venkataiah, B.; Kashinatham, A.Tetrahedron, 1999, 55, 6585.
83 Das, B.; Srinivas, K.V.N.S. Syn. Commun. 2002, 32(19), 3027.
84 Hajipour, A. R.; Mallakpour, S. E. Tetrahedron 1999, 55(8), 2311.
85 Guifa, S.; Xinsheng, L.; Hongjing, W.Synth. Commun. 2002, 32(3), 381.
86 Wu, L.; Huang, Y. Synth. Chem. 1997, 5, 178.
87 Yinjuan, B.; Jun, L.; Haiying, G.Synth. Commun. 2002, 32(16), 2549.
88 张清华，牟其明，陈淑华等，四川大学学报(自然科学版)2002，39(2)321．
89 Y.Peng, H. G. Lai, S. H. Chen, J. Sichuan Uni (nature & science edit), 2003, 44(1), 117.
90 Nakajima, M.; Minyoshi, I.; Kanayama, K. J. Org. Chem. 1999, 64, 2264.
91 Wang, Y.; Sun, j.; Ding, K. Tetrahedron, 2000, 56, 4447.
92 Shunjun, J.; Jianmei, L.; Xinlin, Z. Synth. Commun. 2002, 32(19), 3069.
93 nastas P. T., Williamson T. C., "Green Chemistry" 1, 1996, American Chemical
Society (Library of Catalog-in-Publication Data).
94 杜灿屏，刘鲁生，张恒，“21世纪有机化学发展战略”，化学工业出版社，2002，30-55．
95 金钦汉等，“微波化学” 科学出版社，2001，126-146．
96 Varma, R. S.; Kumar, D.Organic Lett. 1999, 1(5), 697.
97 Bhushan, M.; Virendra, R. Synth. Commun. 2002, 32(11), 1731.
98 朱清时，大学化学，1997，6(12)，7．
99 Yadav J. S., Reddy B. V. S., Reddy R T., Synthetic Commun., 2001, 31(3), 425.
100 Gellis A., Njoya Y., Crozet M. R, Vanelle R, Synthetic Commun., 2001, 31(8), 1267.
101 Ayub J, John C S, Chemical Reviews, 1999, 99 (4), 931.
102 Li D H, Chen S H, Zhao H M. Chemical Research and Application, 1999, 3, 21.
103 张清华，牟其明，陈淑华等．四川大学学报(自然科学版)，2002，39(2)，321
104 Ando T, Yamawaki J, Kawate T, Sumi S. Bull. Chem. Soc. Jpn., 1982, 55, 2504
105 尾崎，田丸谦二，田部活三等．催化剂手册(《催化剂手册》翻泽小组译)，北京：化学工业出版社，1982，268．
106 Kerr G T, Johnson C G. J. Phys. Chem, 1960, 64, 381.
107 Mdrquez H, Plutin A, Rodri guez Y. Synthetic Communications, 2000, 30(6), 1067.
108 Seiji, S.; Takeshi, K.; Yumiko, K. J. Chem. Soc. Perkin Trans. I 1982, 2741.
109 Seiji, S.; Takeshi, N.; Yoshihiro, N. J. Am. Chem. Soc. 1980, 102, 5860.
110 赵志明，胡蓉，陈淑华等，中国化学会全国第九届大环化学暨首届超分子化学学术讨论会论文集，1998，天津．
111 薛翠花 四川大学博士学位论文，2001，30．
112 Tomoyuki, O.; Yayoi, Y.; Yasushi, Y. Bull. Chem. Soc. Jpn. 2001, 74, 2181. b. Yarnabe, T.; Hori, K.; Akagi, K.; Fukui, K. Tetrahedron. 1979, 35, 1065. c. Zheng, Q. T.; Chen, C. E; Huang, Z. T. Tetrahedron. 1997, 53, 10345. d．刘育，戚爱棣，韩宝航，李玉梅，张毅民，陈荣梯．科学通报．1997，42，1516．
113 尤长城，刘育，高等学校化学学报．2000，21，249．b．尤长城，张闵，刘育．化学学报． 2000, 58, 338. c. Liu, Y.; You, C-C.; He, S.; Chen, G-S.; Zhao, Y-L. J. Chem. Soc., Perkin Trans. 2. 2002, 463.
114 Chang, S. K.; Hamilton, A. D. J. Am. Chem. Soc. 1988, 110, 1328. b. Bukownik, R. R.;
Wilicox, C. S. J. Am. Chem. Soc. 1988, 110, 6204.
115 Liu, Y.; Zhang, Y. M.; Sun, S. X.; Li, Y. M.; Chen, R. T. J. Chem. Soc., Perkin Trans. 2. 1997, 1606.
116 a. Sawada, M.; Takai, Y.; Yamada, H.; Nishida, J.; Kaneda, T.; Arakawa, R.; Okamoto, M.; Hirose, K.; Tanaka, T.; Naemura, K. J. Chem. Soc., Perkin Trans. 2. 1998, 701. b. Krishna, P.; Prabhakar, S.; Manoharan, M.; Jemmis, E. D.; Vairamani, M. Chem. Commun. 1999, 1215.
117 Boerrigter, H.; Grare, U; Nissink, J. W. M.; Chrisstoffels, L. A. J.; van der Maas, J.; Verboom, W.; de Jong, F.; Reinhoudt, D. N. J. Org. Chem. 1998, 63, 4174.
118 a. Lee, H. J.; Yoon, I. J.; Yoo, C. U; Pyun, H-J.; Cha, G. S.; Nam, H.Anal. Chem. 2000, 72, 4694. b. Seiichi, N.; Tomoyuki, Y.; Ryo, K.; Yakeshi, S.; Norio, T. Bull. Chem. Soc. Jpn. 2001, 74, 2343.
119 a. Kakeda, Y.; Goto, H. Bull. Chem. Soc. Jpn. 1979, 52, 1920. b. Potluri, V. K.; Maitra, U.J. Org. Chem. 2000, 65, 7764. c. Ayling, A. J.; Broderick, S.; Clare, J. P.; Davis, A. E; Nieves Pérez-Payán, M.; Lahtinen, M.; Nissinen, M. J.; Rissanen, K. Chem. Eur J. 2002, 8, 2197.
120 a. Inoue, Y.; Hakushi, T.; Liu, Y.; Tong, L. H.; Bao, J. S.; Jin, D. S. J. Am. Chem. Soc. 1993, 115, 475. b. Christensen, J. J.; Ruckman, J.; Eatough, D. J.; Izatt, R. M. Thermochim. Acta. 1972, 3, 203. c. Eatough, D. J.; Christensen, J. J.; Izatt, R. M. Thermochim. Acta. 1972, 3, 219.
121 nesi, H. A.; Hildebrend, J. H. J. Am. Chem. Soc. 1949, 71, 2703.
122 郝爱友，童林荟，张复升．化学物理学报．1996，9，450．
123 郝爱友，童林荟，高兴明，张复升．物理化学学报．1995，11，202．
124 刘育，历斌，李白运，陈荣梯．税学通报．1998，43，592．
125 Liu, Y.; Yamamota, K.; Wada, T.; Everitt, S.; Gao, X-M.; Hou, Z-J.; Tong, L-H.; Jiang, S-K.; Wu, H-M. J. Chem. Soc., Perkin Trans. 2. 1998, 1807.
126 刘育，尤长城，张衡益．超分子化学，南开大学出版社，2001．
127 陆国元，胡宏纹．中国科学(B辑)．1996，26，289．
128 薛翠花 四川大学博士学位论文，2001，83．
(b)Aoyama et al. Tetrahedron Lett. 1988, 29, 5271
(c)Ogoshi, H. et al. J. Syn. Org. Chem, Japan. 1989, 47, 514
(d)Aoyama et al. J. Am. Chem. Soc. 1991, 113, 6233
(e)Hayashi, T. et al. J. Am. Chem. Soc. 1993, 115, 2094
(f)Hayashi, T. et al. J. Am. Chem. Soc. 1995, 117, 11606
2. J. M. Lehn, Angew. Chem. Ed. Engl, 1990, 29, 1304.
3. Dugas, H. "Bioorganic Chemistry Frontiers" Vol.2, Springer-Verlay Berlin Heidelbery, 1991, P33, 117
4. Massahiro, I.; Takahiro, S.; Masahisa N. J. Am. Chem Soc. 2003, 125, 1140.
5. Anil, N.; Satish, A.; Umesh, G. Bull. Chem. Soc. Jpn., 2002, 75, 2161-2167.
6. Gyungse P.; John, T. T.; Tomlinson, Matt, S. M. Organic Letters, 2003, 2, 113.
7. Prasanna, S. A.; Mcelenaghan, N. D. Chem. Eur. J. 2002, 8(21), 4935-4945.
8. Rebek, J. Jr.; Askew, B.; Killoran, M.; Nerneth, D.; Lin, F. F. J. Am Chem, Soc 1987,109,2426
9． 陈淑华，罗光荣 《生物有机化学》(四川大学出版社)，1991，318．
10. Marchend, A. P. et al. Tetrahedron 1996, 52(27), 8979.
11. Yamamoto, K.; Yurnioka, H.; Okamoto, Y.; Chikamatsu, H. J. Chem. Soc. Chem. Commun 1987, 168～169
12. Habata, Y.; Bradshaw J. S.; Zhang, X. X.; izatt, R. M. J. Am. Chem. Soc. 1997, 119, 7145～7146
13. (a)Kobuke, Y.; Sumida, Y.; Hayashi, M.; Ogoshi, H. Angew. Chem. Int. Ed. Engl. 1991, 30, 1496
(b)Kobuke, Y.; Satoh, Y. K. J. Am. Chem. Soc, 1992, 114, 789.
(c)Kobuke, Y.; Kobubo, K.; Mumnakata, M. J. Am. Chem. Soc 1995, 117, 12751.
14. (a) Nabeshima, T.: Inaba, T.; Furukawa, N. Tetrahedron Lett, 1987, 28, 6211
(b) Nabeshima, T.: Inaba, T.; Furukawa, N. Hosoya, T.; Yano, Y. Inorg. Chem. 1993, 33, 1407
15. Jones, R.D.; Summerville, D. A.; Basolo. F Chem, Rev. 1979, 79, 139
16． 曹国英，奚祖威 分子催化，1994，8(3)，232
17. (a)Agarwal, D. D.; Bhatnagar, R. E; Jain, R.; Srivastava, S. J. Mol Catal. 1990, 59, 385
(b)Koola, J.D.; Kochi, J. K. Inorg. Chem. 1987, 26, 908
(C)Chatterjee, D.; Bajaj, H. C. et al. J. Mol Catal. 1993, 84, L1-L5
(d)Yoon. H.; Wagler, T. R.; O'Conner, K. J.; Burrows, C. J. J. Am. Chem. Soc 1990, 112, 4568.
18. Liu, J. G.; Xie, F. X.; Zhamg, C. Y.; Tian, Y. E; Ni, S. S. Chinese Chemical Letters 1998, 9(3) 245.
19. Seiji S.; Takahiro N.; Toshiyuki O. J. Am. Chem. Soc. 1981, 103, 111.
20. Akiyo Y.; Takashi H.; Ayako K. Bull. Chem. Soc. Jpn. 2002, 75, 1527.
21. James D C.; Andrew, J. G.; Bosnich B. Chem. Commun. 2003, 392-393.
22. Kyu-Sung J.; Kwang H. S.; Soong-Hyun K. Chemistry Letters, 2002, 1166.
23. Gale, P. A.; Coord. Chem. Rev. 2000, 199, 181.
24. Antonisse, M. M. G.; Reinhoudt, D. N. Chem. Commun. 1998, 443
25 Iao, J-H.; Chen, C-T.; Fang, J-M. Org.. Lett. 2002, 4, 561.
26 (?)en, W. E.; Causey, C. P. J. Org. Chem. 2002, 67, 5963.
27 Kondo, S.; Sakuno, Y.; Yokoyama, T.; Yano, Y. Chem. Lett. 2001, 830.
28 Prohens, R.; Tomàs, S.; Morey, J.; Deyà, P. M.; Balsester, P.; Costa, A. Tetrahedron Lett. 1998, 39, 1063.
29 Tobe, Y.; Sasaki, S.; Mizuno, M.; Hirose, K.; Naemura, K. J. Org. Chem. 1998, 63, 7481.
30 Gunnlaugsson, T.; Davis, A. P.; O'Brien, J. E.; Glynn, M. Org. Lett. 2002, 4, 2449.
31 Lee, D. H.; Lee, H. Y.; Lee, K. H.; Hong, J. I. Chem. Commun. 2001, 1188.
32 Fan, E.; Van Arman, S. A.; Kincaid, S.; Hamilton, A. D. J. Am. Chem. Soc. 1993, 115, 369.
33 Nishizawa, S.; Buhlmann, P.; Zwao, M.; Umezawa, Y.Tetrahedron Lett. 1995, 36, 6483.
34 Büohmann, P.; Nishizawa, S.; Xiao, K. P.; Umezawa, Y. Tetrahedron. 1997, 53, 1647.
35 Xiao, K. P.; Büohmann, P.; Nishizawa, S.; Amemiya, S.; Umezawa, Y. Anal. Chem. 1997, 69, 1038.
36 Kelly, T. R.; Kim, M. H. J. Am. Chem. Soc. 1994, 116, 7072.
37 Jeong, K.; Park, J. W.; Cho, Y. L. Tetrahedron Lett. 1996, 37, 2795.
38 Hamann, B. C.; Branda, N. R..; Rebek Jr, J. Tetrahedron Lett. 1993, 34, 6837.
39 Benito, J. M.; Gómez-Garci a, M.; Jiménez Blanco, J. L. J. Org. Chem. 2001, 66, 1366.
40 Corey, P. C.; William, E. A. J. Org. Chem. 2002, 67, 5963.
41 Hyejae, I.; Sunggoo, Y.; Heon, G. K. Organic Letters, 2002, 4 (17), 2897.
42 Hidekazu, M.; Simon, R.. C.; Ivan, P. Chem. Commun, 2003, 64.
43 Maria, A.; Mercedes, C. C.; Peter, T. J. Org. Chem. 2003, 68, 1097.
44 Bell, T. W.; Hou, Z.; Luo, Y.; Drew, M. G, B.; Chapoteau, E.; Czech, B. P.; Kumar, A. Science (Washington, D. C.). 1995, 269, 671.
45 Craw, J. S.; Cooper, M. D.; Hillier, I. H. J. Chem. Soc., Perkin Trans. 2. 1997, 869.
46 陈淑华，罗光荣 《生物有机化学》(四川大学出版社)，1991，211．
47 Beatriz, B.; Adrian, G. B.; Perla, B. Chem. Eur. J. 2002, 8 (13), 2931.
48 (a)薛翠花，牟其明，李玲，陈淑华．四川大学学报(自然科学版)．2001，38，124．
(b)薛翠花，胡蓉，牟其明，李方，陈淑华．化学学报．2000，58，717．
(c)薛翠花，牟其明，陈淑华．化学学报．2002，60，355．
49 Ming-Hua, X.; Jing, L.; Lin, P. J. Am. Chem. Soc. 2002, 124, 14239.
50 Helma, W.; Matthis C. N.; Matteo, M. C. Chem. Eur. J. 2003, 9(2), 442.
51 Susumu, A.; Michael, L. B.; Chan, S. O. Organic Letters, 2002, 4(24), 4249.
52 Wilen, S. H. Topics in stereochemistry, 1971, 6, 107, New York: John Wiley.
53 Prasad, E N.; Williams, D. J. Intruduction to Nonlinear Optical Effects in Molecules and Polymer, Wiley, New York, 1990.
54 Bhattacharya, S.; Dastidar, P.; Guru, T. N. Chem. Mater., 1994, 6, 531.
55 Tomori, H.; Yoshihara, H.; Ogura, K. Bull. Chem. Soc. Jpn, 1996, 69, 3581.
56 Gedye, R.; Smith, E; Westaway, K. Tetrahedron Lett, 1986, 27(3), 279
57 Gedye, R.; Smith, E; Westaway, K. Can. J Chem. 1958, 66, 17.
58 Bose, A.; Manhas, M.; Gosh, M.; Shah, M.; J. Org. Chem. 1991, 56, 6968
59 Mingos, D. M. P.; Baghurst. D. R. Chem. Soc. Rev. 1991, 20, 1.
60 Galema, S. A. Chem. Soc. Rev. 1997, 26, 233.
61 Chen, S. A.; Tseng, P. H.; Yu, H. M. J. Chin. Chem. Soc. 1997, 44, 169.
62 Dittmer, D. C. Chem. & Industry, 1997, 6 Oct., 779
63 Fan, X. J.; You, J. M.; Tan, G. Z. Progress in Chem. 1998, 10(3), 285.
64 Loupy, A. Topics in Current Chem. 1999, 206, 153.
65 金钦汉；戴树珊；黄卡玛．微波化学(科学出版社)，1999，118．
66 沙耀武；王宇；葛俊．有机化学．2001，21(2)102
67 Abdelkrim, Ben, Allonm; J. Chem. Soc., Chem. Commun. 1987, (7), 386
68 王静；姜凤超 有机化学 2002，22 (3) 212
69 彭游 赖会国 陈淑华等 四川大学学报(自然科学版)2003，40(1)，117．
70 Patil, M. L.; Jnaneshwara, G. K.; Sabde, D. P. Tetrahedron Lett. 1997, 38, 2137.
71 Anil S. G.; Dhananjay P. S.; Murlidhar S. S. Syn. Commun. 2002, 32(10), 1549.
72 Kumar, H. M.; Reddy, B. V.; Reddy, E. J. Tetrahedron Lett. 1999, 40, 2401.
73 Mane, A. S.; Chavan, V. P.; Karale, b. k. Syn. Commun. 2002, 32(17), 2633.
74 Louerat, E; Bougrin, J.; Loupy, A. Heterocycles 1998, 48(1), 234
75 彭游 牟其明 陈淑华等 第四届中国微波化学研讨会论文集 2002，140．
76 Gutierrez, E.; Loupy, A.; Bram, G. Tetrahedron Lett. 1989, 30, 945.
77 Oghaddam, E M.; Ghaffarzadeh, M.; J. Chem. Res., Synop. 1999, 9, 574.
78 Handrakala, M.; Murthy, K.V.V.S.B.S.R.; Kulkani,S.J.J. Chem. 2000, 39, 71.
79 Lingaiah N.; Narender, R.; Dattatray, A. Syn. Commun. 2002, 32(14), 2195.
80 Majid, M.; Dariush, A.; Bagher, M. Syn. Commun. 2002, 32(21), 3325.
81 S.Ravi Kanth, G.Venkat Reddy, V.V.V.N.S. Rama Rao. Syn. Commun. 2002, 32(18), 2849.
82 Das, B.; Venkataiah, B.; Kashinatham, A.Tetrahedron, 1999, 55, 6585.
83 Das, B.; Srinivas, K.V.N.S. Syn. Commun. 2002, 32(19), 3027.
84 Hajipour, A. R.; Mallakpour, S. E. Tetrahedron 1999, 55(8), 2311.
85 Guifa, S.; Xinsheng, L.; Hongjing, W.Synth. Commun. 2002, 32(3), 381.
86 Wu, L.; Huang, Y. Synth. Chem. 1997, 5, 178.
87 Yinjuan, B.; Jun, L.; Haiying, G.Synth. Commun. 2002, 32(16), 2549.
88 张清华，牟其明，陈淑华等，四川大学学报(自然科学版)2002，39(2)321．
89 Y.Peng, H. G. Lai, S. H. Chen, J. Sichuan Uni (nature & science edit), 2003, 44(1), 117.
90 Nakajima, M.; Minyoshi, I.; Kanayama, K. J. Org. Chem. 1999, 64, 2264.
91 Wang, Y.; Sun, j.; Ding, K. Tetrahedron, 2000, 56, 4447.
92 Shunjun, J.; Jianmei, L.; Xinlin, Z. Synth. Commun. 2002, 32(19), 3069.
93 nastas P. T., Williamson T. C., "Green Chemistry" 1, 1996, American Chemical
Society (Library of Catalog-in-Publication Data).
94 杜灿屏，刘鲁生，张恒，“21世纪有机化学发展战略”，化学工业出版社，2002，30-55．
95 金钦汉等，“微波化学” 科学出版社，2001，126-146．
96 Varma, R. S.; Kumar, D.Organic Lett. 1999, 1(5), 697.
97 Bhushan, M.; Virendra, R. Synth. Commun. 2002, 32(11), 1731.
98 朱清时，大学化学，1997，6(12)，7．
99 Yadav J. S., Reddy B. V. S., Reddy R T., Synthetic Commun., 2001, 31(3), 425.
100 Gellis A., Njoya Y., Crozet M. R, Vanelle R, Synthetic Commun., 2001, 31(8), 1267.
101 Ayub J, John C S, Chemical Reviews, 1999, 99 (4), 931.
102 Li D H, Chen S H, Zhao H M. Chemical Research and Application, 1999, 3, 21.
103 张清华，牟其明，陈淑华等．四川大学学报(自然科学版)，2002，39(2)，321
104 Ando T, Yamawaki J, Kawate T, Sumi S. Bull. Chem. Soc. Jpn., 1982, 55, 2504
105 尾崎，田丸谦二，田部活三等．催化剂手册(《催化剂手册》翻泽小组译)，北京：化学工业出版社，1982，268．
106 Kerr G T, Johnson C G. J. Phys. Chem, 1960, 64, 381.
107 Mdrquez H, Plutin A, Rodri guez Y. Synthetic Communications, 2000, 30(6), 1067.
108 Seiji, S.; Takeshi, K.; Yumiko, K. J. Chem. Soc. Perkin Trans. I 1982, 2741.
109 Seiji, S.; Takeshi, N.; Yoshihiro, N. J. Am. Chem. Soc. 1980, 102, 5860.
110 赵志明，胡蓉，陈淑华等，中国化学会全国第九届大环化学暨首届超分子化学学术讨论会论文集，1998，天津．
111 薛翠花 四川大学博士学位论文，2001，30．
112 Tomoyuki, O.; Yayoi, Y.; Yasushi, Y. Bull. Chem. Soc. Jpn. 2001, 74, 2181. b. Yarnabe, T.; Hori, K.; Akagi, K.; Fukui, K. Tetrahedron. 1979, 35, 1065. c. Zheng, Q. T.; Chen, C. E; Huang, Z. T. Tetrahedron. 1997, 53, 10345. d．刘育，戚爱棣，韩宝航，李玉梅，张毅民，陈荣梯．科学通报．1997，42，1516．
113 尤长城，刘育，高等学校化学学报．2000，21，249．b．尤长城，张闵，刘育．化学学报． 2000, 58, 338. c. Liu, Y.; You, C-C.; He, S.; Chen, G-S.; Zhao, Y-L. J. Chem. Soc., Perkin Trans. 2. 2002, 463.
114 Chang, S. K.; Hamilton, A. D. J. Am. Chem. Soc. 1988, 110, 1328. b. Bukownik, R. R.;
Wilicox, C. S. J. Am. Chem. Soc. 1988, 110, 6204.
115 Liu, Y.; Zhang, Y. M.; Sun, S. X.; Li, Y. M.; Chen, R. T. J. Chem. Soc., Perkin Trans. 2. 1997, 1606.
116 a. Sawada, M.; Takai, Y.; Yamada, H.; Nishida, J.; Kaneda, T.; Arakawa, R.; Okamoto, M.; Hirose, K.; Tanaka, T.; Naemura, K. J. Chem. Soc., Perkin Trans. 2. 1998, 701. b. Krishna, P.; Prabhakar, S.; Manoharan, M.; Jemmis, E. D.; Vairamani, M. Chem. Commun. 1999, 1215.
117 Boerrigter, H.; Grare, U; Nissink, J. W. M.; Chrisstoffels, L. A. J.; van der Maas, J.; Verboom, W.; de Jong, F.; Reinhoudt, D. N. J. Org. Chem. 1998, 63, 4174.
118 a. Lee, H. J.; Yoon, I. J.; Yoo, C. U; Pyun, H-J.; Cha, G. S.; Nam, H.Anal. Chem. 2000, 72, 4694. b. Seiichi, N.; Tomoyuki, Y.; Ryo, K.; Yakeshi, S.; Norio, T. Bull. Chem. Soc. Jpn. 2001, 74, 2343.
119 a. Kakeda, Y.; Goto, H. Bull. Chem. Soc. Jpn. 1979, 52, 1920. b. Potluri, V. K.; Maitra, U.J. Org. Chem. 2000, 65, 7764. c. Ayling, A. J.; Broderick, S.; Clare, J. P.; Davis, A. E; Nieves Pérez-Payán, M.; Lahtinen, M.; Nissinen, M. J.; Rissanen, K. Chem. Eur J. 2002, 8, 2197.
120 a. Inoue, Y.; Hakushi, T.; Liu, Y.; Tong, L. H.; Bao, J. S.; Jin, D. S. J. Am. Chem. Soc. 1993, 115, 475. b. Christensen, J. J.; Ruckman, J.; Eatough, D. J.; Izatt, R. M. Thermochim. Acta. 1972, 3, 203. c. Eatough, D. J.; Christensen, J. J.; Izatt, R. M. Thermochim. Acta. 1972, 3, 219.
121 nesi, H. A.; Hildebrend, J. H. J. Am. Chem. Soc. 1949, 71, 2703.
122 郝爱友，童林荟，张复升．化学物理学报．1996，9，450．
123 郝爱友，童林荟，高兴明，张复升．物理化学学报．1995，11，202．
124 刘育，历斌，李白运，陈荣梯．税学通报．1998，43，592．
125 Liu, Y.; Yamamota, K.; Wada, T.; Everitt, S.; Gao, X-M.; Hou, Z-J.; Tong, L-H.; Jiang, S-K.; Wu, H-M. J. Chem. Soc., Perkin Trans. 2. 1998, 1807.
126 刘育，尤长城，张衡益．超分子化学，南开大学出版社，2001．
127 陆国元，胡宏纹．中国科学(B辑)．1996，26，289．
128 薛翠花 四川大学博士学位论文，2001，83．