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Author: 洪三文
Sang-Wen Hon
Thesis Title: N-亞柳胺基酸衍生之三牙配子氧釩錯合物在非對稱酚衍生物偶合反應之研究
Catalytic Asymmetric Coupling of 2-Naphthols by Chiral Tridentate Oxovanadium(IV) Complexes
Advisor: 陳建添
Chen, Chien-Tien
Degree: 博士
Doctor
Department: 化學系
Department of Chemistry
Thesis Publication Year: 2001
Academic Year: 89
Language: 中文
Number of pages: 166
Keywords (in Chinese): 非對稱偶合反應
Keywords (in English): Catalytic Asymmetric Coupling of 2-Naphthols
Thesis Type: Academic thesis/ dissertation
Reference times: Clicks: 416Downloads: 4
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  • 一連串由三牙配子N-3,5-取代基-,N-3,4-苯并-和N-5,6-苯并-亞柳胺基酸所衍生之氧釩(IV)錯合物,可以有效分別扮演各式3-,6-,7-取代-α酚氧化偶合反應,我們針對催化劑的各種製備方法與特性,偶合反應中溶劑與共氧化劑效應,各種α-胺基酸光輔劑的效應,與催化反應機構深入作探討,在許多酚衍生物氧化偶合反應中,我們發展出的催化劑所獲得的鏡像選擇性均比文獻已知方法為高,且此類錯合物穩定性高,製備容易且經濟,是極具價值的研究課題,其中我們以2-羥基-1-苯并柳醛 和2-胺基異戊酸(或苯丙胺酸)所衍生而成的氧釩 (IV)錯合物為催化劑,可以得到1,1’-雙-萘酚產率75~100%,和高達62%的鏡像選擇性,亦是已知非對稱催化方法中最成功的,其初步的研究結果在此發表。

    A series of chiral oxovanadium(IV) complexes derived from tridentate N-3,5-substituted and N-3,4-benzo- and N-5,6-benzo-salicylidene-α-amino acids can serve as efficient catalysts for the enantioselective oxidative couplings of various 3-,6-,7-substituted- 2-naphthols under O2. We take the reseach about the solvent effect,cooxidant effect,amino acid effect….and so on in detail. Our catalyst in the coupling reaction of 2-naphthol is the best methodology as we know. The best scenario involves the use of a vanadyl complex arising from 2-hydroxy-1-naphtholaldehyde and valine (or phenylalanine) in CCl4, leading to BINOLs in good yields (75-100%) and with enantioselectivities of up to 68%.

    背景介紹.............................1 合成BINOL衍生物的方法................5 氧釩錯合物在新型催化反應的重要性.....14 研究與討論...........................18 展望.................................36 參考文獻.............................37 實驗步驟與光譜數據...................41

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