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研究生：	葉倫輔 Lun-Fu Yeh
論文名稱：	有機催化連鎖反應與外消旋化合物之光學分割 Organocatalytic Domino Process and Kinetic Resolution: Synthesis of Functionalized Cyclopentenes
指導教授：	陳焜銘
學位類別：	碩士 Master
系所名稱：	化學系 Department of Chemistry
論文出版年：	2012
畢業學年度：	100
語文別：	中文
論文頁數：	94
中文關鍵詞：	光學分割、有機催化、連鎖反應、Michael加成反應、環戊烯
英文關鍵詞：	Kinetic resolution, Organocatalysis, Cascade, Michael reaction, Cyclopentene
論文種類：	學術論文
相關次數：	點閱：346 下載：2
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有機催化連鎖反應和光學分割結合是很有趣的反應類型。本實驗使用醋酸硝基丙烯酯外消旋混合物和戊二醛，以催化劑50催化，進行SN2’-Michael共軛加成-脫去連鎖反應，得到高立體選擇性四取代基環戊烯衍生物(高達96% ee 和12:1 dr)。回收反應性較低的起始物，同樣得到高光學純度(高達99% ee)。在文獻上，此反應是第一次利用不對稱有機催化經由SN2’-Michael共軛加成-脫去連鎖反應，合成高選擇性環戊烯衍生物，並且得到光學分割效率(s)高達143。

The combination of organocatalytic cascade reaction and kinetic resolution is conceptually new in organocatalytic reaction. Treatment of racemic nitroallylic acetates 87 with glutaraldehyde 90 in the presence of a catalyst 50 to give tetrasubstituted cyclopentenes 118 with high to excellent stereoselectivities (up to 96% ee and 12:1 dr) via sequential SN2'-Michael process. The less reactive enantiomeric substrates were generally recovered with good to excellent optical purities (up to 99% ee). This is the first organocatalytic process for the synthesis of functionalized cyclopentenes with excellent stereoselectivities via an SN2′-Michael conjugate addition-elimination process. The selectivity factors (s) for the reaction ranged from 50 - 143.

第一章  導論 .......................................................1
  1-1 前言 ........................................................1
  1-2 有機催化劑的發展與應用 .......................................3
  1-3 不對稱胺催化反應 .............................................9
  1-4 有機催化劑在連鎖反應的應用 .................................12
  1-5 光學分割反應介紹 .........................................17
  1-6 研究動機 ...................................................21
第二章  實驗結果與討論 ...........................................22
  2-1 不對稱連鎖反應與光學分割 .............................22
     2-1-1  有機催化劑製備 ......................................23
     2-1-2  起始物nitroallylic acetate 的製備 ........................25
     2-1-3  溶劑效應(1) .........................................26
     2-1-4  戊二醛之當量數及催化劑量效應.........................28
     2-1-5  添加劑效應(1) .......................................29
     2-1-6  催化劑篩選 ..........................................32
     2-1-7  溶劑效應(2) .........................................34
     2-1-8  添加劑效應(2) .......................................36
     2-1-9  HPLC光譜分析 ......................................38
     2-1-10 取代基效應 ..........................................39
  2-2 絕對立體組態鑑定 .........................................41
     2-2-1  起始物立體組態鑑定 ..................................41
     2-2-2  產物立體組態鑑定 ....................................43
  2-3 反應機構探討 .............................................43
  2-4 結論 .....................................................46
第三章  實驗部分 .................................................47
  3-1 分析儀器及基本實驗操作 ...................................47
  3-2 實驗步驟及光譜數據 .......................................49
     3-2-1  有機催化劑92製備 ...................................49
     3-2-2  起始物nitroallylic acetate 87製備 ........................50
     3-2-3  不對稱有機催化連鎖反應及光學分割反應之實驗步驟 ....51
  3-3 參考文獻 .................................................67
附錄一、 1H-NMR、13C-NMR 光譜 ..................................70

                                

(1) List, B. Angew. Chem. Int. Ed. 2010, 49, 1730.
(2) List, B.; Lerner, R. A.; Barbas III, C. F. J. Am. Chem. Soc. 2000, 122, 2395.
(3) MacMillan, D. W. C. Nature 2008, 455, 304.
(4) List, B. Chem. Commun. 2006, 819.
(5) Bertelsen, S.; Jørgensen, K. A. Chem. Soc. Rev. 2009, 38, 2178.
(6) Grondal, C.; Jeanty, M.; Enders, D. Nat. Chem. 2010, 2, 167.
(7) Enders, D.; Huttl, M. R. M.; Grondal, C.; Raabe, G. Nature 2006, 441, 861.
(8) Rendler, S.; MacMillan, D. W. C. J. Am. Chem. Soc. 2010, 132, 5027.
(9) Kaneko, S.; Yoshino, T.; Katoh, T.; Terashima, S. Tetrahedron 1998, 54, 5471.
(10) Ishikawa, H.; Suzuki, T.; Hayashi, Y. Angew. Chem. Int. Ed. 2009, 48, 1304.
(11) Vedejs, E.; Jure, M. Angew. Chem. Int. Ed. 2005, 44, 3974.
(12) Martin, V. S.; Woodard, S. S.; Katsuki, T.; Yamada, Y.; Ikeda, M.; Sharpless, K. B. J. Am. Chem. SOC. 1981, 103, 6237.
(13) Coric, I.; Muller, S.; List, B. J. Am. Chem. Soc. 2010, 132, 17370.
(14) During the preparation of the manuscript, Prof. Brenner-Moyer reported the first example of organocascade kinetic resolution, see: McGarraugh, P. G.; Brenner-Moyer, S. E. Org. Lett. 2011, 13, 6460.
(15) (a) Vedejs, E.; Chen, X. J. Am. Chem. Soc. 1996, 118, 1809. (b) Oriyama, T.; Hori, Y.; Imai, K.; Sasaki, R. Tetrahedron Lett. 1996, 37, 8543. (c) Matsumura, Y.; Maki, T.; Murakami, S.; Onomura, O. J. Am. Chem. Soc. 2003, 125, 2052. (d) Kawabata, T.; Nagato, M.; Takasu, K.; Fuji, K. J. Am. Chem. Soc. 1997, 119, 3169-3170. (e) Miller, S. J.; Copeland, G. T.; Papaioannou, N.; Horstmann, T. E.; Ruel, E. M. J. Am. Chem. Soc. 1998, 120, 1629.
(16) For selected O-acylation reactions, see: (a) Shiina, I.; Nakata, K.; Ono, K.; Sugimoto, M.; Sekiguchi, A. Chem.-Eur. J. 2010, 16, 167. (b) Müller, C. E.; Wanka, L.; Jewell, K.; Schreiner, P. R. Angew. Chem., Int. Ed. 2008, 47, 6180. (c) Li, X.; Liu, P.; Houk, K. N.; Birman, V. B. J. Am. Chem. Soc. 2008, 130, 13836. (d) Birman, V. B.; Guo, L. Org. Lett. 2006, 8, 4859. (e) Kawabata, T.; Nagato, M.; Takasu, K.; Fuji, K. J. Am. Chem. Soc. 1997, 119, 3169. For selected N-acylation reactions, see: (f) Arseniyadis, S.; Valleix, A.; Wagner, A.; Mioskowski, C. Angew. Chem., Int. Ed. 2004, 43, 3314. (g) Kanta De, C.; Klauber, E. G.; Seidel, D. J. Am. Chem. Soc. 2009, 131, 17060.
(17) For selected catalytic silylation, see: (a) Zhao, Y.; Mitra, A. W.; Hoveyda, A. H.; Snapper, M. L. Angew. Chem., Int. Ed. 2007, 46, 8471. (b) Isobe, T.; Fukuda, K.; Araki, Y.; Ishikawa, T. Chem. Commun. 2001, 243.
(18) (a) Xie, J.-W.; Fan, L.-P.; Su, H.; Li, X.-S.; Xu, D.-C. Org. Biomol. Chem. 2010, 8, 2117. (b) Yu, J.; Chen, W.-J.; Gong, L.-Z. Org. Lett. 2010, 12, 4050. (c) Shimada, N.; Ashburn, B. O.; Basak, A. K.; Bow, W. F.; Vicic, D. A.; Tius, M. A. Chem. Commun. 2010, 46, 3774.
(19) (a) Reddy, R. J.; Chen, K. Org. Lett. 2011, 13, 1458. (b) Reddy, R. J.; Lee, P.-H.; Magar, D. R.; Chen, J.-H.; Chen, K. Eur. J. Org. Chem. 2012, 353.
(20) For the use of glutaraldehyde in organocatalysis, see: (a) He, Z.-Q.; Han, B.; Li, R.; Wu, L.; Chen, Y.-C. Org. Biomol. Chem. 2010, 8, 755. (b) Hong, B. C.; Nimje, R. Y.; Sadani, A. A.; Liao, J.-H. Org. Lett. 2008, 10, 2345. (c) Hazelard, D.; Ishikawa, H.; Hashizume, D.; Koshino, H.; Hayashi, Y. Org. Lett. 2008, 10, 1445.
(21) For selected synthesis of cyclopentane derivatives, see (a) Zu, L.; Li, H.; Xie, H.; Wang, J.; Jiang, W.; Tang, Y.; Wang, W. Angew. Chem., Int. Ed. 2007, 46, 3732. (b) Ibrahem, I.; Zhao, G.-L.; Rios, R.; Vesely, J.; Sunden, H.; Dziedzic, P.; Cordova, A. Chem.-Eur. J. 2008, 14, 7867. (c) Zhao, G.-L.; Ibrahem, I.; Dziedzic, P.; Sun, J.; Bonneau, C.; Cordova, A. Chem.-Eur. J. 2008, 14, 10007. (d) Tan, B.; Shi, Z.; Chua, P. J.; Zhong, G. Org. Lett. 2008, 10, 3425. (e) Tan, B.; Chua, P. J.; Zeng, X.; Min, L.; Zhong, G. Org. Lett. 2008, 10, 3489.
(22) (a) Wang, J.; Li, H.; Xie, H.; Zu, L.; Shen, X.; Wang, W. Angew.Chem., Int. Ed. 2007, 46, 9050. (b) Rueping, M.; Kuenkel, A.; Tato, F.; Bats, J. W. Angew. Chem., Int. Ed. 2009, 48, 3699. (c) Chiang, P. C.; Kaeobamrung, J.; Bode, J. W. J. Am. Chem. Soc. 2007, 129, 3520. (d) Chiang, P. C.; Rommel, M.; Bode, J. W. J. Am. Chem. Soc. 2009, 131, 8714. (e) Hong, B. C.; Dange, N. S.; Hsu, C.-S.; Liao, J.-H. Org. Lett. 2010, 12, 4812.
(23) Chang, C.; Li, S. H.; Reddy, R. J.; Chen, K. Adv. Synth. Catal. 2009, 351, 1273
(24) Kagan, H. B.; Fiaud, J. C. Topics in Stereochemistry; Eliel, E. L., Fiaud, J. C., Eds.; Wiley: New York, 1988; Vol. 18, p 249.
(25) Hayashi, Y.; Okano, T.; Aratake, S.; Hazelard, D. Angew. Chem., Int. Ed. 2007, 46, 4922.
(26) Baldwin, J. E. J. Chem. Soc., Chem. Commun. 1976, 734.
(27) Rueping, M.; Parra, A. Org. Lett. 2010, 12, 5281.
(28) Many attempts to derivatize 119 for the absolute stereochemistry determination failed. Tentative assignment (i.e. cis) was made according to the previous observation, see ref. 19 and 25.
(29) 張智亮，國立臺灣師範大學博士論文，2010
(30) 李佩勳，國立臺灣師範大學碩士論文，2011

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