臺灣博碩士論文加值系統

我們成功以鈀金屬催化含氮炔類化合物進行分子內合環形成環戊
烷取代吡咯衍生物，且使用微波反應器輔助可以有效提升產率，最高可
達92%。此方法可應用於合成藥物Ramipril 中的重要結構。

Hydroamination of N-(2-ethynylcyclopentyl)sulfonamide to
give non-aromatic 2,3-dihydropyrroles was achieved by using
PdCl2 as the catalyst. With microwave-assisted heating, up to 92%
isolated yield was obtained from this intramolecular 5-endodig
cyclization. The cyclopentane-fused 2,3-dihydropyrroles were
transformed into the corresponding N-tosyl-pyrrolidine-2-
carboxylic acids.

總目錄
中文摘要 I
英文摘要 II
總目錄 III
圖目錄 V
流程圖目錄 VI
表目錄 VII
附圖目錄 VIII
第一章 序論 1
1-1 前言 1
1-2 含氮雜環的合成 2
1-3 研究動機 8
第二章 結果與討論 9
2-1 起始物的製備 9
2-2 金屬催化合環反應的結果 14
2-2-1 最佳反應條件 14
2-2-2鈀金屬催化環戊烷取代含氮炔類的合環反應 16
2-2-3合成cyclopentane-fused N-tosyl-pyrrolidine-2-carboxylic acid 19
2-2-4合成具高共軛系統吡咯衍生物 20
第三章 結論 24
第四章 實驗部分 25
4-1溶媒及處理過程 25
4-2實驗器材與儀器 26
4-3實驗步驟 29
第五章 參考文獻 88

第五章 參考文獻
1. (a) Comprehensive Heterocyclic Chemistry III, ed. A. R. Katritzky, C. A. Ramsden, E. F. V. Scriven and R. J. K. Taylor, Elsevier Science, 2008, vol. 3; (b) J. A. Joule and K. Mills, in Heterocyclic Chemistry, John Wiley & Sons, 2010, pp. 587–608; (c) J. Bergman and T. Janosik, in Modern Heterocyclic Chemistry, ed. J. Alvarez-Builla, J. J. Vaquero and J. Barluenga, Wiley-VCH, 2011, ch. 4.
2. (a) D. C. Peters, S. Noble and G. L. Plosker, Drugs, 1998, 56, 871; (b) F. Brion, C. Marie, P. Mackiewicz, J. M. Roul and J. Buendia, Tetrahedron Lett., 1992, 33, 4889; (c) H. Shionoiri, I. Takasaki, K. Minamisawa, H. Ishizuka, K. Konno, H. Naganuma, K. Sasahara and Y. Kawahara, Hypertens. Res., 2001, 24, 235.
3. (a) J. E. Frampton and D. H. Peters, Drugs, 1995, 49, 440; (b) G. C. M. Kondaiah, M. Vivekanandareddy, L. A. Reddy, S. A. Anurkar, V. M. Gurav, M. Ravikumar, A. Bhattacharya and R. Bandichhor, Synth. Commun., 2011, 41, 1186.
4. (a) P. Morain, P. H. Boeijinga, A. Demazieres, G. De Nanteuil and R. Luthringer, Neuropsychobiology, 2007, 55, 176; (b) G. Bellemere, P. Morain, H. Vaudry and S. Jegou, J. Neurochem., 2003, 84, 919; (c) P. Morain, P. Lestage, G. D. Nanteuil, R. Jochemsen, J.-L. Robin, D. Guez and P.-A. Boyer, CNS Drug Rev., 2002, 8, 31.
5. (a) M. Murakami, Y. Okita, H. Matsuda, T. Okino and K. Yamaguchi, Tetrahedron Lett., 1994, 35, 3129; (b) M. Murakami, K. Ishida, T. Okino, Y. Okita, H. Matsuda and K. Yamaguchi, Tetrahedron Lett., 1995, 36, 2785; (c) J. L. Rios Steiner, M. Murakami and A. Tulinsky, J. Am. Chem. Soc., 1998, 120, 597; (d) S. Kodani, K. Ishida and M. Murakami, J. Nat. Prod., 1998, 61, 1046; (e) K. Ishida, K. Okita, H. Matsuda, T. Okino and M. Murakami, Tetrahedron, 1999, 55, 10971; (f ) K. Ersmark, J. R. Del Valle and S. Hanessian, Angew. Chem., Int. Ed., 2008, 47, 1202.
6. Recent examples catalyzed by Pd: (a) M. Jash, B. Das and C. Chowdhury, J. Org. Chem., 2016, 81, 10987; (b) E. A. Filatova, A. F. Pozharskii, A. V. Gulevskaya and V. A. Ozeryanskii, J. Org. Chem., 2015, 80, 872; (c) B. Yao, Q. Wang and J. Zhu, Chem. – Eur. J., 2015, 21, 7413; (d) R. Shen, T. Kusakabe, K. Takahashi and K. Kato, Org. Biomol. Chem., 2014, 12, 4602; (e) C. Zheng, J. J. Chen and R. Fan, Org. Lett., 2014, 16, 816; (f ) G. Xia, X. Han and X. Lu, Org. Lett., 2014, 16, 2058; (g) B. Yao, Q. Wang and J. Zhu, Chem. – Eur. J., 2014, 20, 12255; (h) D. Janreddy, V. Kavala, C.-W. Kuo, T.-S. Kuo, C.-H. He and C.-F. Yao, Tetrahedron Lett., 2013, 69, 3323; (i) X.-F. Xia, N. Wang, L.-L. Zhang, X.-R. Song, X.-T. Liu and Y.-M. Liang, J. Org. Chem., 2012, 77, 9163.
7. Recent examples catalyzed by Cu: (a) S. Cacchi, G. Fabrizi and L. M. Parisi, Org. Lett., 2003, 5, 3843; (b) K. Hiroya, S. Itoh and T. Sakamoto, J. Org. Chem., 2004, 69, 1126; (c) N. Matsuda, K. Hirano, T. Satoh and M. Miura, J. Org. Chem., 2012, 77, 617; (d) J. Gao, Y. Shao, J. Zhu, J. Zhu, H. Mao, X. Wang and X. Lv, J. Org. Chem., 2014, 79, 9000; (e) J. Gao, Y. Shao, J. Zhu, J. Zhu, H. Mao, X. Wang and X. Lv, J. Org. Chem., 2014, 79, 9000; (f ) Y. Xing, G. Sheng, J. Wang, P. Lu and Y. Wang, Org. Lett., 2014, 16, 1244; (g) J. Tang, B. Xu, X. Mao, H. Yang, X. Wang and X. Lv, J. Org. Chem., 2015, 80, 11108; (h) J. Yu, D. Zhang-Negrerie and Y. Du, Org. Lett., 2016, 18, 3322; (i) H. E. Ho, K. Oniwa, Y. Yamamoto and T. Jin, Org. Lett., 2016, 18, 2487.
8. Recent examples catalyzed by Au: (a) K. C. Majumdar, S. Hazra and B. Roy, Tetrahedron Lett., 2011, 52, 6697; (b) K. Hirano, Y. Inaba, N. Takahashi, M. Shimano, S. Oishi, N. Fujii and H. Ohno, J. Org. Chem., 2011, 76, 1212; (c) M. Muuronen, J. E. Perea-Buceta, M. Nieger, M. Patzschke and J. Helaja, Organometallics, 2012, 31, 4320; (d) O. S. Morozov, A. V. Lunchev, A. A. Bush, A. A. Tukov, A. F. Asachenko, V. N. Khrustalev, S. S. Zalesskiy, V. P. Ananikov and M. S. Nechaev, Angew. Chem., Int. Ed., 2013, 52, 11835; (e) P. P. Sharp, M. G. Banwell, J. Renner, K. Lohmann and A. C. Willis, Org. Lett., 2013, 15, 2616; (f) J. E. Perea-Buceta, T. Wirtanen, O.-V. Laukkanen, M. K. Mäkelä, M. Nieger, M. Melchionna, N. Huittinen, J. A. Lopez-Sanchez and J. Helaja, Angew. Chem., Int. Ed., 2013, 52, 11835; (g) B. V. S. Reddy, M. R. Reddy, S. Yarlagadda, C. R. Reddy, G. R. Kumar, J. S. Yadav and B. Sridhar, J. Org. Chem., 2015, 80, 8807; (h) S. Liang, L. Hammond, B. Xu and G. B. Hammond, Adv. Synth. Catal., 2016, 358, 3313.
9. (a) S. Miaskiewicz, J.-M. Weibel, P. Pale and A. Blanc, Org. Lett., 2016, 18, 844; (b) S. Miaskiewicz, B. Gaillard, N. Kern, J.-M. Weibel, P. Pale and A. Blanc, Angew. Chem., Int. Ed., 2016, 55, 9088; (c) A. Galván, J. Calleja, F. J. Fañanás and F. Rodríguez, Chem. – Eur. J., 2015, 21, 3409; (d) Y.-F. Yu, C. Shu, B. Zhou, J.-Q. Li, J.-M. Zhou and L. W. Ye, Chem. Commun., 2015, 51, 2126; (e) W. V. Rossom, Y. Matsushita, K. Ariga and J. P. Hill, RSC Adv., 2014, 4, 4897.
10. (a) O. Mitsunobu, Synthesis, 1981, 1; (b) J. M. Barks, G. G. Weingarten and D. W. Knight, J. Chem. Soc., Perkin Trans. 1, 2000, 3469.
11. A. Zhdanko and M. E. Maier, Angew. Chem., Int. Ed., 2014, 53, 7760
12. B. C. J. van Esseveldta, F. L. van Delfta, J. M. M. Smitsb, R. de Gelderb and F. P. J. T. Rutjes, Synlett, 2003, 2354.
13. A. Nuhricha and J. Moulines, Tetrahedron, 1991, 47, 3075.