Basic Search / Detailed Display

Author: 李治毅
Li, Zhi-Yi
Thesis Title: 一價銠金屬/掌性雙環雙烯配基錯合物催化環狀α,β-不飽和氮-磺醯基酮亞胺與有機硼試劑進行高鏡像選擇性及高位性選擇性的不對稱加成反應
Highly Enantioselective and Regioselective Addition of Organoboron Reagents to Cyclic α,β-Unsaturated N-Sulfonyl Ketimines Catalyzed by Rh (Ι)/Chiral Diene Complexes
Advisor: 吳學亮
Wu, Hsyueh-Liang
Degree: 碩士
Master
Department: 化學系
Department of Chemistry
Thesis Publication Year: 2017
Academic Year: 105
Language: 中文
Number of pages: 263
Keywords (in Chinese): 一價銠金屬
Keywords (in English): Rh
DOI URL: https://doi.org/10.6345/NTNU202203008
Thesis Type: Academic thesis/ dissertation
Reference times: Clicks: 131Downloads: 0
Share:
School Collection Retrieve National Library Collection Retrieve Error Report
  • 本論文敘述以一價銠金屬和掌性雙環雙烯配基形成錯合物為催化劑,催化有機硼試劑與亞胺,進行具位像選擇性及鏡像選擇性的不對稱加成反應。
    使用一價銠金屬和掌性雙環雙烯配基L6a形成的錯合物為催化劑,以1,4-二噁烷為溶劑碳酸鉀為添加劑,催化芳香基硼酸與α,β-不飽和亞胺21,進行不對稱1,4-加成反應,產物22產率最高可達95%,鏡像超越值最高可達99% ee。
    以一價銠金屬和掌性雙環雙烯配基L1a形成的錯合物為催化劑,以乙腈為溶劑水為添加劑,進行烯丙基三氟硼酸鉀鹽對亞胺21的1,2-加成反應,產物32產率最高可達99%,鏡像超越值最高可達99.5% ee。

    A highly enantioselective and regioselective addition of organo boron reagents to cyclic α,β-unsaturated N-sulfonyl ketimines catalyzed by in situ generated Rh (Ι) catalyst is described.
    The 1,4-addition reaction of arylboronic acids proceeds with excellent regioselectivity to offer 1,4 adducts in good yields (up to 95% yield) and stereoselectivity (up to 99% ee) in the presence of Rh (Ι) catalyst.
    Futhermore, in the presence of Rh(Ι)/L1a the enantioselective allyation of cyclic N-sulfonyl ketimine of 21 proceeds via 1,2-addition fashion, offering the corresponding products in up to 99% yield and 99.5% ee.

    表目錄 ii 圖目錄 iv 謝誌 vii 中文摘要 viii Abstract x 中英對照表 xii 第一章 緒論 1 第二章 文獻回顧1 (硼酸對烯酮或亞胺進行不對稱加成的研究) 4 第三章 實驗結果與討論1 (芳香基硼酸加成) 16 第四章 文獻回顧2 (具共軛系統的亞胺進行不對稱1,2-加成反應) 39 第五章 結果與討論2 (三氟硼酸鉀鹽加成) 43 第六章 實驗部分 74 第七章 參考文獻 123 附 錄 125 X-Ray ORTEP 解析圖譜及數據 126 1H及13C NMR圖譜 173

    1. Toxicol Sci. 2009, 110, 4–30.
    2. Stinson, S. C. Chem. Eng. News. 1992, 70, 46–79.
    3. Sakai, N.; Hayashi, H.; Miyaura, N. Organometallics.1997, 16, 4229–4231.
    4. Takaya, Y.; Ogasawara, M.; Hayashi, T.; Sakai, M.; Miyaura, N. J. Am. Chem. Soc. 1998, 120, 5579–5580.Wei-Ting Wei,Jiann-Yih Yeh,Ting-Shen Kuo,and Hsyueh-Liang Wu
    5. Ueyama, K.; Tokunaga, N.; Yoshida, K.; Hayashi, T. J. Am. Chem. Soc. 2003, 125, 11508–11509.
    6. Liu, C.-C.; Janmanchi, D.; Chen, C.-C.; Wu, H.-L. Eur. J. Org. Chem. 2012, 13, 2503–2507.
    7.Wei, W.-T.; Yeh, J.-Y.; Kuo, T.-S.; Wu, H.-L. Chem. Eur. J. 2011, 17, 11405–11409.
    8. 廖柏翔 (2014)。銠(I)金屬催化烯基硼酸試劑對α,β-不飽和酮類化合物的1,4-不對稱加成反應。碩士論文,國立台灣師範大學化學研究所,臺北,臺灣。
    9. Chen, C.-C.; Gopula, B.; Syu, J.-F.; Pan, J.-H.; Kuo, T.-S.; Wu, P.-Y.; Julian, P. Henschke and Wu, H.-L. J. Org. Chem. 2014, 79, 8077-8085.
    10. Lee, A.; Kim, H. J. Am. Chem. Soc. 2015, 137, 11250–11253.
    11. Zhang, Y.-F.; Chen, D.;Chen, W.-W.; Xu, M.-H. Org. Lett. 2016, 18, 2726−2729.
    12. Wei, W.-T.; Yeh, J.-Y; Kuo, T.-S; Wu, H.-L. Chem. Eur. J. 2011, 17, 11405–11409.
    13. Abele, S.; Inauen, R.; Spielvogel, D.; Moessner, C. J. Org.
    Chem. 2012, 77, 4765–4773.
    14. Hirner, S.; Kolb, A.; Westmeier, J.; Gebhardt, S.; Middel, S.; Harms, K.; Zezschwitz, P. Org. Lett. 2014, 16, 3162−3165.
    15. Luo, Y.; Hepburn, H. B.; Chotsaeng, N.; Lam, H.-W. Angew. Chem. Int. Ed. 2012, 51, 8309−8313.
    16. 江佩芬 (2016)。一價銠金屬/掌性雙環 [2.2.1] 雙烯催化芳香亞胺不對稱烯丙基化反應。碩士論文,國立台灣師範大學化學研究所,臺北,臺灣。
    17. Tian, P.; Dong, H.-Q.; Lin, G.-Q. ACS Catal. 2012, 2, 95−119.

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