研究生: |
陳佳杏 Chen, Chia Hsing |
---|---|
論文名稱: |
有機金屬鋅催化炔醯胺類與Chloramine-T進行氯胺化反應和有機金屬金催化兩分子炔醯胺類與烯類進行立體選擇性[2+2+2]環加成反應 Zinc-Catalyzed Chloroamination reaction of Ynamides and Chloramine-T And Gold-Catalyzed Regiocontrolled [2+2+2]-Cycloadditions of Two Terminal Ynamides with Vinyl ether |
指導教授: |
劉瑞雄
Liu, Rai Shung |
口試委員: |
吳明忠
李文泰 |
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: | 2016 |
畢業學年度: | 104 |
語文別: | 中文 |
論文頁數: | 187 |
中文關鍵詞: | 鋅金屬催化 、氯胺化反應 、金金屬催化 、[2+2+2]合環 |
外文關鍵詞: | Zinc catalyst, Gold catalyst, chloroamination, cycloadditions |
相關次數: | 點閱:3 下載:0 |
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第一章
經由有效的鋅催化劑,將中端炔和Chloramine-T在室溫下進行氯胺化,在溫和的條件下,得到高產率的雙氯亞胺形式的產物((Z)-2,2-dichloro-N-methyl-N-(methylsulfonyl)-2-phenyl-N'-tosylacetimidamide),產物還具備的兩個缺電子基團,容易與其他不同的親核試劑進行下一步反應。
第二章
利用金金屬催化劑,催化兩個末端炔醯胺和烯類進行立體選擇性[2+2+2]-環加成反應,建構出多取代苯環的衍生物,這種新的環加成反應的效用適用在廣泛範圍的炔醯胺和乙烯基乙醚或2-甲氧基丙烯有優異的區域選擇性與表現,且目前較少例子是使用烯烴,來進行[2+2+2]合環反應。
PART 1
The synthesis of (Z)-2,2-dichloro-N-methyl-N-(methyl-sulfonyl) -2-phenyl-N'-tosylacetimidamide, an efficient zinc catalyzed reaction enhancing the reactivity for the chloroamination of alkynes with Chloramine-T at room temperature, is described with moderate to good yields. The electron-deficient character of the azomethine group of polyhalogenaldimines promotes their interactions with numerous nucleophiles, which could be used for further reactions.
PART 2
This part of the dissertation deals with the gold-catalyzed regiocontrolled [2+2+2]cycloadditions of two ynamides and vinyl ether constructing polysubstituted benzene derivatives. The utility of this new cycloaddition is manifested in the excellent regioselectivity with a wide range of scope of applicable ynamides as well as vinyl ether. And there are few examples using alkene for [2+2+2]cyclization reactions.
第一章
[1]Liu, X.-Y.; Gao, P.; Shen, Y.-W.; Liang, Y.-M., Adv Synth & Catal 2011, 353 (17), 3157-3160.
[2](a) Krivdin, L. B.; Chernyshev, K. A.; Rosentsveig, G. N.; Ushakova, I. V.; Rosentsveig, I. B.; Levkovskaya, G. G., Magn. Reson. Chem. 2007, 45 (11), 980-984.(b) Levkovskaya, G. G.; Drozdova, T. I.; Rozentsveig, I. B.; Mirskova, A. N., Usp. Khim. 1999, 68 (7), 638-662.
[3](a)Rozentsveig, I. B.; Serykh, V. Y.; Chernysheva, G. N.; Kondrashov, E. V.; Fedotova, A. I.; Ushakov, I. A.; Tretyakov, E. V.; Romanenko, G. V., Eur. J. Org. Chem. 2014, (29), 6547-6557.
(b)Rozentsveig, G. N.; Popov, A. V.; Rozentsveig, I. B.; Levkovskaya, G. G., Russ. J. Org. Chem. 2011, 47 (4), 520-522.
[4]Rozentsveig, I. B.; Rozentsveig, G. N.; Serykh, V. Y.; Chernyshev, K. A.; Levkovskaya, G. G., Eur. J. Org. Chem. 2011, (23), 4415-4421.
[5]Rozentsveig, I. B.; Serykh, V. Y.; Chernysheva, G. N.; Chernyshev, K. A.; Kondrashov, E. V.; Tretyakov, E. V.; Romanenko, G. V., Chem. Eur. J. 2013, (2), 368-375.
[6]Shindo, M.; Itoh, K.; Tsuchiya, C.; Shishido, K., Anionic, Org. Letters 2002, 4 (18), 3119-3121.
[7]Mukherjee, A.; Dateer, R. B.; Chaudhuri, R.; Bhunia, S.; Karad, S. N.; Liu,R.-S., J. Am. Chem. Soc. 2011, 133 (39), 15372-15375.
[8]Pawar, S. K.; Sahani, R. L.; Liu, R.-S., Chem. Eur. J. 2015, 21 (30), 10843-10850.
[9]Mamane, V.; Hannen, P.; Furstner, A., Chem. Eur. J. 2004, 10 (18), 4556-4575.
[10]Yeh,M.-C.P.;Liang,C.-J.;Chen,H.-F.;Weng, Y.-T., Adv Synth & Catal 2015, 357 (14-15), 3242-3254.
[11]Hamada, T.; Ye, X.; Stahl, S. S., J. Am. Chem. Soc. 2008, 130 (3), 833-835
[12]Murase, H.; Senda, K.; Senoo, M.; Hata, T.; Urabe, H., Chem. Eur. J. 2014, 20 (1), 317-322.
第二章
[1] Heller, B.; Hapke, M., Chem. Soc. Rev. 2007, 36 (7), 1085-1094.
[2] Dominguez, G.; Perez-Castells, J., Chem. Soc. Rev. 2011, 40 (7), 3430-3444.
[3] (a) Kissane, M.; Maguire, A. R. Chem. Soc. Rev. 2010, 39, 845. (b) Martin, J. N.; Jones, R. C. F.Padwa, A., Pearson, W. H., John Wiley & Sons: Hoboken, NJ, 2003; Chapter 1. (c) Gothelf, K. V.Kobayashi, S., Jørgensen, K. A., Wiley-VCH: Weinheim, Germany, 2002; Chapter 6. (d) Kanemasa,S. Kobayashi, S., Jørgensen, K. A., Wiley-VCH: Weinheim, Germany, 2002; Chapter 7.(e) Haaban, M. R.; El-Sayed, R.; Elwahy, A. H. M., Tetrahedron 2011, 67 (34), 6095-6130.(f) Lautens, M.; Tam, W.; Lautens, J. C.; Edwards, L. G.; Crudden, C. M.; Smith, A. C., J. Am. Chem. Soc. 1995, 117 (26), 6863-6879.(g) Tanaka, D.; Sato, Y.; Mori, M., J. Am. Chem. Soc. 2007, 129 (25), 7730-7731.(h) Seo, J.; Chui, H. M. P.; Heeg, M. J.; Montgomery, J., J. Am. Chem. Soc. 1999, 121 (2), 476-477.(i) Shibata, T.; Tahara, Y.-k., J. Am. Chem. Soc. 2006, 128 (36), 11766-11767.(j) Ogoshi, S.; Nishimura, A.; Ohashi, M., Org. Letters 2010, 12 (15), 3450-3452
[4] a) K. Undheim, T. Benneche, in Comprehensive Heterocyclic Chemistry II, Vol. 6 (Eds.: A. R.Katritzky, C. W. Rees, E. F. V. Scriven, A. McKillop), Pergamon, Oxford, 1996, p. 93 –231; b)Michael, J. P. Nat. Prod. Rep. 2005, 22, 627. c) Joule, J. A.; Mills, K. in Heterocyclic Chemistry,4th ed.. Blackwell, Cambridge, 2000, p. 194 –232; d) Erian, A.W. Chem. Rev. 1993, 93, 1991.
[5] a) [2 + 2 + 2] Cycloaddition reactions are also domino reactions. For applications and examples,see: L. F. Tietze, G. Brasche and K. M. Gericke, Domino Reactions in Organic Synthesis, Wiley-VCH, Weinheim, 2006 and cited references. b) Reppe, W.; Schichting, O.; Klager, K.; Toepel, T.Justus Liebigs Ann. Chem. 1948, 560, 1–92.
[6] Ikeda, S.; Mori, N.; Sato, Y., J. Am. Chem. Soc. 1997, 119 (20), 4779-4780.
[7]Louie, J.; Gibby, J. E.; Farnworth, M. V.; Tekavec, T. N., J. Am. Chem. Soc. 2002, 124 (51), 15188-15189.
[8]Kezuka, S.; Tanaka, S.; Ohe, T.; Nakaya, Y.; Takeuchi, R.,. J. Org. Chem. 2006, 71 (2), 543-552.
[9]Qiu, Z.; Xie, Z., Angew. Chem. Int. Ed. 2009, 48 (31), 5729-5732.
[10]Dateer, R. B.; Shaibu, B. S.; Liu, R.-S., Angew. Chem. Int. Ed. 2012, 51 (1), 113-117.
[11]Karad, S. N.; Liu, R.-S., Angew. Chem. Int. Ed. 2014, 53 (34), 9072-9076.
[12]Chen, Y.-L.; Sharma, P.; Liu, R.-S., Chem. Commun. 2016, 52 (15), 3187-3190.
[13]A. E. Goetz, N. K. Garg. Nature. Chem. 2013, 5, 54.
[14]L. Q. Yang, K. B. Wang, C. Y. Li, Chem. Eur.J, 2013, 14, 2775.