Solanoeclepin A 的右半部之三環系統與其衍生物之合成研究

簡易檢索 / 詳目顯示

回結果列表

研究生：	莊聖頡 Chuang, Sheng-Chieh
論文名稱：	Solanoeclepin A 的右半部之三環系統與其衍生物之合成研究 Synthetic Studies on a Ticyclic Ring System Analogous to the Right Hand Segment of the Solanoeclepin A
指導教授：	磯部稔 Minoru Isobe
口試委員:	汪炳鈞 Uang, Biing-Jiun 鍾文聖 Chung, Wen-Sheng
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：	2012
畢業學年度：	100
語文別：	英文
論文頁數：	120
中文關鍵詞：	全合成、天然物
外文關鍵詞：	total synthesis, natural compounds
相關次數：	點閱：3 下載：0
分享至:	分享至facebook 分享至twitter

查詢本校圖書館目錄查詢臺灣博碩士論文知識加值系統勘誤回報

中文摘要:

天然物solanoeclepin A，研究發現其具有刺激馬鈴薯中的囊腫線蟲提早孵化的功能，可運用在農業病蟲害防治上。本論文中，我們專注在solanoeclepin A中的三員環[5.2.1.01,6]癸烷骨架之建構，其包含四,五,六員環和三個四級不對稱中心。

我們經由[2,3]-Wittig 反應完成C-1四級碳的建構，並且藉由氯化二茂鈦催化環氧乙烷4進行分子內自由基環合反應建構三環[5.2.2.01,6]十一烷5的骨架。

合成途徑以Hajos-Parrish 酮 1 為起始物，進行Horner-Wadsworth-Emmons (HWE) 反應合成反式不飽和酯 2。其經由官能基轉換可獲得前驅物3 隨後進行[2,3]-Wittig rearrangement 反應產生炔丙基醇4 與其異構物。最後以氯化二茂鈦催化自由基環化反應建構三員環[5.2.2.01,6]十一烷的骨架。

Abstract:

Solanoeclepin A shows significant hatch-stimulating activity for the potato cyst nematodes. In this thesis, we focused on the synthesis of tricyclo[5.2.1.01,6]decane skeleton of solanoeclepin A, including four-, five- and six-membered ring bearing three consecutive quaternary stereocenters.

We have achieved the quarternalization of C-1 carbon via [2,3]-Wittig rearrangement and the construction of tricyclo[5.2.2.01,6]undecene system 5 through titanocene-mediated radical cyclization from epoxide 4.

The synthesis started from Hajos-Parrish ketone 1 and it was converted to E-unsaturated ester 2 in a few steps including Horner-Wadsworth-Emmons (HWE) reaction. After multi-steps synthesis, the precursor 3 was subjected to [2,3]-Wittig rearrangement conditions to yield 4 and its isomer. Next, titanocene-mediated radical cyclization afforded the tricyclo[5.2.2.01,6]undecene framework.

Chapter I. Introduction ………….……………………………………………………………………………1
I-1. The Potato Eelworm Hatching Agents…………………………………………………1 
I-2. Introduction of Solanoeclepin A…………………………………………………………2 
I-2-1. Origin of Solanoeclepin A……………………………………………………………………2 
I-2-2. Synthetic Reviews of Solanoeclepin A………………………………………3 
I-3. Purpose and Research Proposal………………………………………………………………8 
I-3-1. Retrosynthetic Analysis (I) of Solanoeclepin A …………8 
I-3-2. Hosomi-SakuraiReaction……………………………………………………………………………9
I-3-3. [3,3]-Sigmatropic Rearrangement……………………………………………………10 
I-3-4. Retrosynthetic Analysis (II) of Solanoeclepin A…………12 
I-3-5. Horner-Wadsworth-Emmons Reaction…………………………………………………14 
I-3-6. [2,3]-Wittig Rearrangement…………………………………………………………………15 
Chapter II. Results and Discussion…………………………………………………………… 17
II-1. Synthetic Route (I)- [3,3]-Sigmatropic Rearrangement………………………………………………………………………………………………………………………17 
II-1-1. Synthesis of Precursor of [3,3]- Sigmatropic Rearrangemen…………………………………………………………………………………………………………………………17 
II-1-2. Claisen Rearrangement……………………………………………………………………………20
II-1-3. Johnson-Claisen Rearrangement………………………………………………………23 
II-1-4. Ireland-Claisen Rearrangement………………………………………………………29 
II-2. Synthetic Route (II)- [2,3]-Wittig Rearrangement………………………………………………………………………………………………………………………31 
II-2-1. Synthesis of Precursor of [2,3]-Wittig Rearrangement………….31 
II-2-2. Quarternalization of C-1 carbon via [2,3]-Wittig Rearrangement………………………………………………………………………………………………………………………34 
II-2-3. Anionic Construction of Tricyclo[5.2.1.01,6]decane Skeleton……………………………………………………………………………………………………………………………………37 
II-2-4. Cationic Construction of Tricyclo[5.2.1.01,6]decane Skeleton……………………………………………………………………………………………………………………………………38 
II-2-5. Radical Cyclization of Tricyclo[5.2.1.01,6]decane Skeleton……………………………………………………………………………………………………………………………………40 
II-3. Conclusion………………………………………………………………………………………………………………45 
Chapter III. Experimental and Reference…………………………………………………47
III-1. General Information……………………………………………………………………………………47
III-2. Experiment Procedure ………………………………………………………………………………49
III-3. Reference………………………………………………………………………………………………………………66
Appendix……………………………………………………………………………………………………………………………………69

                                

1. Baunacke, W. E. Arb. Biol. Bund Anst. 1923, 11, 185.
2. (a) Todd, A. R.; Calam, C. T.; Raistrick, H. Biochem. J. 1949, 45, 513. (b) Calam, C. T.; Todd, A. R.; Waring, W. S. Biochem. J. 1949, 45, 520. (d) Russell, P. B.; Todd, A. R.; Waring, W. S. Biochem. J. 1949, 45, 528.
3. a) J. G. Mulder, P. Diepenhorst, I. E. M. Brüggemann-Rotgans, PCT Int. Appl.WO 93/02,083. (b) Mulder, J. G.; Diepenhorst, P.; Plieger, P. Chem Abstr. 1993, 118, 5844.
4. Schenk, H.; Driessen, R. A. J.; De Gelder, R.; Goutbitz, K.; Nieboer, H.; Brüggemann- Rotgans, I. E. M.; Diepenhorst, P. Croat. Chem. 1999, 72, 593.
5. (a) Jefford, C. W.; Sledeski, A. W.; Boukouvalas, J. Helv. Chim. Acta 1989, 72, 1362. (b) Jefford, C. W.; Sledeski, A. W.; Rossier, J. C.; Boukouvalas, J. Tetrahedron Lett. 1990, 31, 5741.
6. (a) Brière, J. F.; Richard H. B.; Jorg C. J.; Angeline E.; Hiemstra, H. Eur. J. Org. Chem. 2001, 2371. (b) Hue, B. T. B.; Dijkink, J.; Kuiper, S.; Schaik, S.; J. Maarseveen, H.; Hiemstra, H. Eur. J. Org. Chem. 2006, 127.
7. Tanino, K.; Takahashi, M.; Tomata, Y.; Tokura, H.; Uehara, T.; Narabu, T.; Miyashita, M. Nature Chem. 2011, 3, 484.
8. Tanino. K.; Tomata, Y.; Shiina, Y.; Miyashita, M. Eur. J. Org. Chem. 2006, 328.
9. Takema.; Adachi, M.; Toshio, N. Chem. Lett. 2012, 41, 287.
10. Adachi, M.; Komada, T.; Nishikawa, T. J. Org. Chem. 2011, 76, 6942.
11. (a) Stork, G.; Tang, P. C.; Casey, M.; Goodman, B.; Toyota, M. J. Am. Chem. 2005, 127, 16255. (b) Kaliappan, K. P.; Ravikumar, V. Org. Lett. 2007, 9, 2417.
12. Hosomi, A.; Sakurai, H. Tetrahedron Lett. 1976, 1295.
13. Saito, T.; Nishimoto, Y.; Ysauda, M.; Bada, A. J. Org. Chem. 2006, 71, 8516
14. (a) Bennett, G. B. Synthesis 1977, 589. (b) Zieger, F. E. Acc. Chem. Res. 1977, 10, 227.
15. Claisen, L. Chem. Ber. 1912, 45, 3157.
16. Johnson, W. S.; Werthemann, L.; Bartlett, W. R.; Brockson, T.J.; Li, T. T.; Faulkner, D. J.; Petersen, M. R. J. Am. Chem. Soc. 1970, 92, 741.
17. Feldman, K. S.; Masters, K. M. J. Org. Chem. 1999, 64, 8945.
18. (a) Ireland, R. E.; Mueller, R. H. J. Am. Chem. Soc. 1972, 94, 5897. (b) Ireland, R. E.; Mueller, R. H.; Willard, A. K. J. Am. Chem. Soc. 1976, 98, 2868.
19. Hatcher, M. A.; Posner, G. H. Tetrahedron Lett. 2002, 43, 5009.
20. Alejandro, F. B.; Jos , F. Q. M.; Elena M.; S nchez, E. M.; Arteaga, J. F. Eur. J. Org. Chm. 2006, 1627.
21. (a) Nakai, T.; Mikami, K. Chem. Rev. 1986, 86, 885. (b) Sugimura, T.; Paquette, L. A. J. Am. Chem. Soc. 1987, 109, 3017.
22. Rao, A. S.; Eds. B. M.; Trost, I. F. Comp. Org. Syn. 1990, 3, 357.
23. Blanchette, M. A.; Choy, W.; Davis, J. T.; Essenfeld, A. P.; Masamune, S.; Roush, W. R.; Sakai, T. Tetrahedron Lett. 1984, 25, 2183.
24. Chochrek, P.; Tyrlik, A.; Michalak, K.; Wicha, J. Tetrahedron Lett. 2006, 47, 6017.
25. Wadsworth, W. Org. React. 1977, 25, 73.
26. (a) Leopold, H.; Hoffmann, H. M. R.; Wippel, H. G. Chem. Ber. 1958, 91, 61.
(b) Horner, L.; Hoffmann, H. M. R.; Wippel, H. G.; Klahre, G. Chem. Ber. 1959, 92, 2499.
27. (a) Wadsworth, W. S.; Emmons, W. D. J. Am. Chem. Soc. 1961, 83, 1733.
(b) Wadsworth, W. S.; Emmons, W. D. Organic Syntheses, 1973, 5, 547.
28. Wadsworth, W. S. Org. React. 1977, 25, 253.
29. Boutagy, J.; Thomas, R. Chem. Rev. 1974, 74, 87-99.
30. Kelly, S. E. Comp. Org. Syn. 1991, 1, 729-817.
31. Maryanoff B. E.; Reitz, A. B. Chem. Rev. 1989, 89, 863-927.
32. (a) Nakai, T. Tetrahedron Lett. 1993, 34, 5923. (b) Takeshi, N.; Koichi, M. Chem. Rev. 1986, 86, 885. (c) Tsai, D. J. S.; Midland, M. M. J. Org. Chem. 1984, 49, 1843.
33. Tsubuki, M.; Okita, H.; Honda, T. J. Chem. Soc. Chem. Commun. 1995, 20, 2135.
34. Hajos, Z. G.; Parrish, D. R. J. Org. Chem. 1974, 39; 1615.
35. Mckeon, J. E.; Fitton, P.; Griswold, A. A. Tetrahedron 1972, 28, 227.
36. Tsao, K. T.; Isobe, M. Org. Lett. 2010, 12, 5338.
37. (a) Watanabe, W. H.; Conlon, L. E. J. Am. Chem. Soc. 1957, 79, 2828. (b) Church, R. F.; Ireland, R. E.; Marshall, J. A. J. Org. Chem. 1966, 31, 2526.
38. Wei, X.; Lonenz, J. C.; Kapadia, S.; Saha, A.; Haddad, N.; Busacca, C.; Senanayake, C. H. J. org. Chem. 2007, 72, 4250.
39. Luche, J. L. J. Am. Chem. Soc. 1978, 100, 2226.

全文公開日期本全文未授權公開 (校內網路)
全文公開日期本全文未授權公開 (校外網路)

簡易檢索 / 詳目顯示

相關論文