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: 416 Downloads: 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%.
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