Basic Search / Detailed Display

Author: 黃崑致
Thesis Title: I.銠(I)金屬結合掌性配位體催化不對稱1,4-加成在-Nitrostyrenes化合物及應用在3,4-二氫異喹啉和(S)-SKF 38393的形式合成。II.銠(I)金屬結合掌性配位體催化不對稱1,4-加成在-Nitroacrylate化合物。
Advisor: 吳學亮
Degree: 碩士
Master
Department: 化學系
Department of Chemistry
Thesis Publication Year: 2013
Academic Year: 101
Language: 中文
Number of pages: 175
Keywords (in Chinese): 銠(I)金屬
Thesis Type: Academic thesis/ dissertation
Reference times: Clicks: 53Downloads: 0
Share:
School Collection Retrieve National Library Collection Retrieve Error Report
  • 第一部分:敘述以銠(I)金屬掌性雙烯為配基(L4)錯合物催化芳香基硼酸試劑(Arylboronic acid)進行不對稱芳香基加成反應合成出一系列具有不對稱中心之雙芳香環硝基甲烷類化合物(Diarylnitroethane)。此反應可以不同芳香基硼酸試劑和-硝基苯乙烯(-nitrostyrene)進行反應,而得到不錯的產率和高立體選擇性的加成產物,其鏡性超越值最高可達到97%。此合成方法最後也利用在合成藥物3,4-二氫異喹啉(3,4-dihydroisoquinoline)以及(S)-SKF 38393上。
    第二部分:敘述以銠(I)金屬掌性雙烯為配基(L4)錯合物,催化芳香基硼酸試劑(Arylboronic acid)進行不對稱芳香基加成反應至-硝基丙烯酸酯(-Nitroacrylate),實驗結果可以的到不錯的產率,以及良好的鏡像選擇性,進一步合成出-胺基酸(-amino acid)的前驅物。

    Part 1:Chiral diarylnitroethane were prepared from the asymmetric addition of a range of arylboronic acids to -nitrostyrene in the presence of Rh(I) diene complex.
    This process offers the 1,4-adducts in good yields and excellent enantioselectivities (ee value up to 97%) for various arylboronic acids and -nitrostyrene.
    This synthesis method is also used in the synthesis of 3,4-dihydroisoquinoline and (S)-SKF 38393.
    Part 2:The asymmetric addition of phenylboronic acids to -nitroacrylate in the presence of Rh(I) diene complex. This process offers the 1,4-adducts in good yields and excellent enantioselectivities(ee value up to 95%) for phenylboronic acids and -nitroacrylate. Further synthesis of 2,2-amino acid precursors.

    縮寫對照表……………………………………………………………I 中文摘要………………………………………………………………II 英文摘要………………………………………………………………III 第一章:緒論……………………………………………………………1 第二章:掌性樟腦行雙烯配基合成……………………………………25 第三章:結果與討論……………………………………………………29 第四章:結論……………………………………………………………51 第五章:實驗部分………………………………………………………52 參考文獻………………………………………………………………94 附錄……………………………………………………………………97 X-ray ORTEP 解析圖譜及數據 1H及13C NMR圖譜

    1. a) Seyden-penne J. In “Chiral Auxiliaries and Ligands in Asymmetric Synthesis”, John-wiley and sons, New York, 1995. b)Calne, D. B.; Sandlar, M. Nature 1970, 226, 21 c)Stinson, S. C. Chem. Eng. News 1992, 70,46.
    2. a) D. A. Evans, J. Bartroli, T. L. Shih, J. Am. Chem. Soc. 1981, 103, 2127-2129; b) D. A. Evans, M. D. Ennis, D. J. Mathre, J. Am. Chem. Soc. 1982, 104, 1737-1739; c) D. A. Evans, K. T. Chapman, J. Bisaha, J. Am. Chem. Soc. 1984, 106, 4261-4263; d) D. A. Evans, K. T. Chapman, D. T. Hung, A. T. Kawaguchi, Angew. Chem. Int. Ed. 1987, 26, 1184–1186.
    3. T. Katsuki, K. B. Sharpless, J. Am. Chem. Soc. 1980, 102, 5974.
    4. a) R. Noyori, T. Okhuma, M. Kitamura, H. Takaya, N. Sayo, H. Kumobayashi, S. Akuragawa, J. Am. Chem. Soc. 1987, 109, 5856-5858. b) B. D. Vineyard, W. S. Knowles, M. J. Sabacky, G. L. Bachman, D. J. Weinkauff, J. Am. Chem. Soc. 1977, 99, 5946-5952.
    5. P. Tian, H. Q. Dong, G. Q. Lin, ACS Catal. 2012, 2, 95−119.
    6. a) Y. Takaya, M. Ogasawara, T. Hayashi, M. Sakai, N. Miyaura, J. Am. Chem. Soc. 1998, 120, 5579-5580. b) J. G. Boiteau, A. J. Minnaard, B. L. Feringa, J. Org. Chem. 2003, 68, 9481-9484. c) J. Chen, J. Chen, F. Lang, X. Zhang, L. Cun, J. Zhu, J. Deng, J. Liao, J. Am. Chem. Soc. 2010, 132, 4552–4553. d) B. G. Guillaume, T. Hayashi, J. Org. Chem. 2006, 71, 8957-8960. e) T. Thaler, L. N. Guo, Andreas K. Steib, M. Raducan, K. Karaghiosoff, P. Mayer, P. Knochel, Org. Lett. 2011, 13, 3182-3185. f ) F. Lang, D. Li, J. Chen, J. Chen, L. Li, L. Cun, J. Zhu, J. Deng , J. Liao, Adv. Synth. Catal. 2010, 352, 843-846. g) T. Minuth, Mike M. K. Boysen, Org. Lett. 2009, 11, 4212-4215.
    7. M. Sakai, H. Hayashi, N. Miyaura, Organometallics 1997, 16, 4229-4231.
    8. Y. Takaya, M. Ogasawara, T. Hayashi, M. Sakai, N. Miyaura, J. Am. Chem. Soc. 1998, 120, 5579-5580.
    9. D. Walsh, Nature. 1947, 159, 712 – 713.
    10. a) M. J. S. Dewar, Bull. Chem. Soc. Fr. 1951, 18, C71–C79; b) M. J. S. Dewar, H. C. Longuet-Higgins, Proc. Royal Acad. Sci. Ser. A. 1952, 214, 482–493.
    11. F. R. Hartley, Chem. Rev. 1973, 73, 163 – 189.
    12. a) H. C. Volger, M. M. P. Gaasbeek, H. Hogeveen, K. Vrieze, Inorg. Chim. Acta. 1969, 3, 145 – 150; b) R. Cramer, J. Am. Chem. Soc. 1967, 89, 4621 – 4626.
    13. a) T. Hayashi, K. Ueyama, N. Tokunaga, K. Yoshida, J. Am. Chem. Soc. 2003, 125, 11508-11509. b) M. K. Brown,E. J. Corey, Org. lett. 2010, 12, 172-175.
    14. a) L. M. Omer, Int. Clin. Pharmacol. Ther. Toxicol. 1982, 20, 320-326; b) In The Chemistry and Biology of Isoquinoline Alkaloids, (Eds:J. D. Phillipson, M. F. Roberts, M. H. Zenk), Springer, Berlin, 1985. c) In Medicinal Natural Products, (Ed: P. M. Dewick) WILEY-VCH, Weiheim, 2002, pp. 315-346; d) J. D. Scott, R. M. Williams, Chem. Rev. 2002, 102, 1669-1730. e) K. W. Bentley, Nat. Proad. Rep. 2006, 23, 444-463.
    15. a) C. Kaiser, P. A. Dandridge, E. Garvey, R. A. Hahn, H. M. Sarau, P. E. Setler, L. S. Bass, J. Med. Chem. 1982, 25, 697-703; b) J. L. Neumeyer, N. Baindur, J. Yuan, G. Booth, P. Seeman, H. B. Niznik, J. Med. Chem. 1990, 33, 521-526; c) I. Pettersson, T. Liljefors, K. Boegesoe, J. Med. Chem. 1990, 33, 2197-2204; d) J. L. Neumeyer, N. Baindur, H. B. Niznik, H. C. Guan, P. Seeman, J. Med. Chem. 1991, 34, 3366-3371. e) J. H. Shah, S. Izenwasser, B. Geter-Douglass, J. M. Witkin, A. H. Newman, J. Med. Chem. 1995, 38, 4284-4293; f) W.-L. Wu, D. A. Burnett, R. Spring, W. J. Greenlee, M. Smith, L. Favreau, A. Fawzi, H. Zhang, and J. E. Lachowicz, J. Med. Chem. 2005, 48, 680-693.
    16. a) T. Y. Liu, H. L. Cui, Q. Chai, J. Long, B. J. Li, Y. Wu, L. S. Ding, Y. C. Chen, Chem. Commun., 2007, 2228-2230; b) H. Zhang, Y. H. Liao, W. C. Yuan, X. M. Zhang, Eur. J. Org. Chem. 2010, 3215–3218; c) Y. Sohtome, B. Shin, N. Horitsugi, R. Takagi, K. Noguchi, K. Nagasawa, Angew. Chem. Int. Ed. 2010, 49, 7299 –7303.
    17. a) In Conjugate Addition Reaction in Organic Synthesis, (Ed: P. Perlmutter), Pergamon Press, Oxford, 1992; b) H.-G. Schmalz, in Comprehensive Organic Synthesis, Vol. 4, Chapter 1.5. (Eds: B.M.Trost, I. Fleming), Pergamon: Oxford, 1991; c) B. E. Rossiter, N. M. Swingle, Chem. Rev. 1992, 92, 771-808; d) K. Tomioka, Y. Nagaoka, in Comprehensive Asymmetric Catalysis, Chapter 31.1. (Eds: E. N. Jacobsen, A. Pfaltz, H. Yamamoto), springer-Verlag: Berlin, 1999; e) M. Yamaguchi, in Comprehensive Asymmetric Catalysis, Chapter 31.2. (Eds: E. N. Jacobsen, A. Pfaltz, H. Yamamoto) , springer-Verlag: Berlin, 1999; f) N. Krausse, A. Hoffmann-Roder, Synthesis 2001, 171-196.
    18. a) Y. Takaya, M. Ogasawara, T. Hayashi, M. Sakai N. Miyaura, J. Am. Chem. Soc. 1998, 120, 5579-5580; b) Y. Takaya, T. Senda, H. Kurushima, M. Ogasawara, T. Hayashi, Tetrahedron: Asymmetry 1999, 10, 4047–4056; c) S. Sakuma, M. Sakai, R. Itooka, N. Miyaura, J. Org. Chem. 2000, 65, 5951-5955; d) T. Senda, M. Ogasawara, T. Hayashi, J. Org. Chem. 2001, 66, 6852-6856.
    19. a) N. Miyaura, in Organoboranes for syntheses, (Eds: P. V. Ramachandran, H. C. Brown), American Chmical Society, Washington, 2001, pp. 94-107; b) T. Hayashi, K. Yamasaki, Chem. Rev. 2003, 103, 2829−2844; c) T. Hayashi, Pure. Appl. Chem. 2004, 76, 465-475.
    20. a) T. Hayashi, T. Senda, M. Ogasawara, J. Am. Chem. Soc. 2000, 122, 10716-10717; b) L. Dong, Y. J. Xu, L. F. Cun, X. Cui, A. Q. Mi, Y. Z. Jiang, L. Z. Gong, Org. lett. 2005, 7, 4285-4288; c) L. Dong, Y. J. Xu, W. C. Yuan, X. Cui, L. F. Cun, L. Z. Gong, Eur. J. Org. Chem. 2006, 4093–4105.
    21. Z. Q. Wang, C. G. Feng, S. S. Zhang, M. H. Xu, G. Q. Lin, Angew. Chem. Int. Ed. 2010, 49, 5780 –5783.
    22. F. Lang, G. Chen, L. Li, J. Xing, F. Han, L. Cun, J. Liao, Chem. Eur. J. 2011, 17, 5242–5245.
    23. F. Xue, D. Wang, X. Li, B. Wan, J. Org. Chem. 2012, 77, 3071−3081.
    24. C. Cativiela, M. D. D´ıaz-de-Villegas, J. A. Ga´lvez, J. Org. Chem. 1994, 59, 2497-2250.
    25. Chi, Y.; Gellman, S. H. J. Am. Chem. Soc. 2006, 128, 6804–6805.
    26. N. J. A. Martin, X. Cheng, B. List, J. Am. Chem. Soc. 2008, 130, 13862–13863.
    27. a) C. C. Liu, D Janmanchi, C. C. Chen, H. L. Wu. Eur. J. Org. Chem. 2012, 2503–2507. b) W. T. Wei, J. Y. Yeh, T. S. Kuo, H. L. Wu. Chem. Eur. J. 2011, 17, 11405 – 11409. c) Y. C. Chung, D. Janmanchi, H. L. Wu. Org. Lett. 2012, 14, 2766-2769.
    28. R. C. Griffith, R. J. Gentile, R. C. Robichaud, J. Frankenheim. J. Med. Chem. 1984, 27, 995-1003.

    無法下載圖示 This full text is not authorized to be published.
    QR CODE