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完整後設資料紀錄
DC 欄位 | 值 | 語言 |
---|---|---|
dc.contributor.advisor | 邱靜雯(Ching-Wen Chiu) | |
dc.contributor.author | Ding-Nan Shih | en |
dc.contributor.author | 施定男 | zh_TW |
dc.date.accessioned | 2021-06-16T17:31:40Z | - |
dc.date.available | 2025-03-05 | |
dc.date.copyright | 2020-03-05 | |
dc.date.issued | 2020 | |
dc.date.submitted | 2020-03-02 | |
dc.identifier.citation | 1. Knowles, W. S.; Sabacky, M. J. Catalytic asymmetric hydrogenation employing a soluble, optically active, rhodium complex. Chem. Commun. (London), 1968, 1445-1446.
2. Brown, H. C.; Bigley, D. B. Bis-3-methyl-2-butylborane as a selective reagent for the reduction of representative functional groups. J. Am. Chem. Soc., 1961, 83, 486-486. 3. Corey, E. J.; Bakshi, R. K.; Shibata, S. Highly enantioselective borane reduction of ketones catalyzed by chiral oxazaborolidines. Mechanism and synthetic implications. J. Am. Chem. Soc., 1987, 109, 5551-5553. 4. Corey, E. J.; Shibata, T.; Lee, T. W. Asymmetric Diels−Alder reactions catalyzed by a triflic acid activated chiral oxazaborolidine. J. Am. Chem. Soc., 2002, 124, 3808-3809. 5. Liu, D.; Hong, S.; Corey, E. J. Enantioselective synthesis of bridged- or fused-ring bicyclic ketones by a catalytic asymmetric Michael addition pathway. J. Am. Chem. Soc., 2006, 128, 8160-8161. 6. Chen, J.; Lalancette, R. A.; Jäkle, F. Synthesis and Lewis acid properties of a ferrocene-based planar-chiral borenium cation. Chem. Commun., 2013, 49, 4893-4895. 7. Lam, J.; Günther, B. A. R.; Farrell, J. M.; Eisenberger, P.; Bestvater, B. P.; Newman, P. D.; Melen, R. L.; Crudden, C. M.; Stephan, D. W. Chiral carbene–borane adducts: precursors for borenium catalysts for asymmetric FLP hydrogenations. Dalton Trans., 2016, 45, 15303-15316. 8. Süsse, L.; Hermeke, J.; Oestreich, M. The asymmetric Piers hydrosilylation. J. Am. Chem. Soc., 2016, 138, 6940-6943. 9. Prokofjevs, A.; Kampf, J. W.; Solovyev, A.; Curran, D. P.; Vedejs, E. Weakly stabilized primary borenium cations and their dicationic dimers. J. Am. Chem. Soc., 2013, 135, 15686-15689. 10. Kong, L.; Lu, W.; Li, Y.; Ganguly, R.; Kinjo, R. Isolation of a diborane(6) dication: formation and cleavage of an electron-precise B(sp3)–B(sp3) Bond. J. Am. Chem. Soc., 2016, 138, 8623-8629. 11. Arnold, N.; Braunschweig, H.; Dewhurst, R. D.; Hupp, F.; Radacki, K.; Trumpp, A. Desymmetrizing electron-deficient diboranes(4): diverse products and their reactivity. Chem. Eur. J., 2016, 22, 13927-13934. 12. Evans, D. A.; Bartroli, J.; Shih, T. L. Enantioselective aldol condensations. 2. Erythro-selective chiral aldol condensations via boron enolates. J. Am. Chem. Soc., 1981, 103, 2127-2129. 13. Evans, D. A.; Ennis, M. D.; Mathre, D. J. Asymmetric alkylation reactions of chiral imide enolates. A practical approach to the enantioselective synthesis of .alpha.-substituted carboxylic acid derivatives. J. Am. Chem. Soc., 1982, 104, 1737-1739. 14. Evans, D. A.; Chapman, K. T.; Bisaha, J. New asymmetric Diels-Alder cycloaddition reactions. Chiral , -unsaturated carboximides as practical chiral acrylate and crotonate dienophile synthons. J. Am. Chem. Soc., 1984, 106, 4261-4263. 15. Tseng, H.-C.; Shen, C.-T.; Matsumoto, K.; Shih, D.-N.; Liu, Y.-H.; Peng, S.-M.; Yamaguchi, S.; Lin, Y.-F.; Chiu, C.-W. [η5-Cp*B-Mes]+: A masked potent boron lewis acid. Organometallics, 2019, 38, 4516-4521. 16. Katayama, H.; Kamigaito, M.; Sawamoto, M., In-Situ Direct Analysis of the Growing Species by 119Sn NMR Spectroscopy: Living Cationic Polymerization of Isobutyl Vinyl Ether with HCl/SnCl4/nBu4NCl. Macromolecules 1998, 31 (15), 4703-4709. | |
dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/64138 | - |
dc.description.abstract | 不對稱催化對於天然產物的合成非常重要。至今為止,已有大量過渡金屬為基底的催化劑已被成功開發用來做各種不對稱催化。在近幾年中,也有以主族元素為基底作為不對稱催化劑的文獻被刊登,其中又以Corey-Bakshi-Shibata的硼雜噁唑烷催化劑最為出色,其不對稱催化劑在還原醛類及酮類的反應中具有極高的轉換效率及鏡像選擇性。受其啟發後,我們也製備了一系列的掌性二聚體硼陽離子催化劑,其催化劑的特點在於它包含了立障大的五甲基茂取代基和掌性噁唑烷酮配體,而五甲基茂取代基的功能在於可以有效避免硼中心被過度配位,而我們選用掌性噁唑烷酮的原因在於它容易取得且易去質子化,這對我們的合成路徑非常有幫助。我們以一系列的中性掌性二聚體硼化合物透過in-situ產生催化劑的方式催化Diels-Alder反應來測試其催化效力,且發現這類催化劑在反應中確實能導入立體選擇性,也發現了催化劑取代基和親鹵試劑的不同會影響產物的光學純度。最後,我們也做了低溫1H NMR實驗來驗證在反應中確實生成了掌性二聚體硼陽離子,且此掌性硼陽離子能催化不對稱Diels-Alder反應。 | zh_TW |
dc.description.abstract | Asymmetric catalysis is crucial for natural product synthesis. Thus, a considerable amount of synthetic efforts have been devoted into the design of transition metal-based catalysts for enantioselective synthesis. In the past few years, chiral catalysts focusing on the s- and p-block elements have also emerged. Inspired by the highly efficient Corey-Bakshi-Shibata catalyst in various asymmetric transformations, we have prepared a series of chiral boron-based dimers consisting of bulky Cp* (1,2,3,4,5-Pentamethylcyclopentadiene) and chiral auxiliary oxazolidinone ligands. While the commercially available chiral oxazolidinone can be easily deprotonated and added to the boron center, the incorporation of electron-rich and steric protective Cp* group was found to be critical in preventing over-substitution at the boron. We found that the chirality can be transferred to the product of Diels-Alder reaction via an in-situ generated cationic diboron catalyst. Furthermore, the enantioselectivity is sensitive towards the substituents of oxazolidinone and halophiles. Finally, the observed asymmetric Diels-Alder reaction was proposed to be associated with a cyclic diboron mono-cation, whose generation under reaction condition was also confirmed by low-temperature 1H NMR studies. | en |
dc.description.provenance | Made available in DSpace on 2021-06-16T17:31:40Z (GMT). No. of bitstreams: 1 ntu-109-R06223183-1.pdf: 3959221 bytes, checksum: 506b36efb119fff98dc9f2270f2cd441 (MD5) Previous issue date: 2020 | en |
dc.description.tableofcontents | 誌謝 i
摘要 ii Abstract iii Work Distribution iv Contents v List of Figures vii List of Schemes ix List of Tables x Chapter 1. Introduction 11 1.1 Transition Metal Catalysts for Asymmetric Synthesis 11 1.2 Boron Containing Chiral Catalysts 12 1.3 Diboron System 15 1.4 Chiral Auxiliary: Oxazolidinone 17 1.5 Molecular Design 18 Chapter 2. Results and Discussions 19 2.1 Synthesis of chiral N-chloroborane 19 2.2 Syntheses and Characterizations of N-Chloroborane Dimer (1) 25 2.2.1 (R)/(S)-4-Benzyl-Oxazolidinone Substituted N-Chloroborane Dimer ((R)/(S)-1a) 25 2.2.2 (R)-4-Benzyl-5,5-Dimethyl-Oxazolidinone Substituted N-Chloroborane Dimer ((R)-1b) 27 2.2.3 (S)-4-Phenyl-Oxazolidinone Substituted N-Chloroborane Dimer ((S)-1c) 27 2.2.4 (S)-4-Phenyl-5,5-Dimethyl-Oxazolidinone Substituted N-Chloroborane Dimer ((S)-1d) 28 2.2.5 (S)-4-Tert-Butyl-Oxazolidinone Substituted N-Chloroborane Dimer ((S)-1e) 29 2.3 Chloride Bridged N-Diboron Cation ([2][Al(OC(CF3)3)4]) 31 2.4 Oxazolidinone Substituted Hypercoordinate Chiral N-Boron Cation ([3][AlCl4]) 34 2.5 Reactivity Studies 37 2.5.1 Optimization of Catalytic Asymmetric Diels-Alder Reaction 37 2.5.2 Reaction of 1c and Halophiles 38 2.5.3 Cyanosilylation of Benzaldehyde Catalyzed by (S)-[2d][B(C6F5)4] 44 Chapter 3. Conclusion 45 Chapter 4. Experimental Section 47 References 60 Chapter 5. Supporting Information 62 5.1 Appendix 62 5.1.1 Crystal Data 62 5.1.1.1 Crystal data for (R)-1a (ic19325) 62 5.1.1.2 Crystal data for (S)-1a (ic19541) 67 5.1.1.3 Crystal data for (S)-1c (ic19789) 72 5.1.1.4 Crystal data for (S)-1d (ic19694) 77 5.1.1.5 Crystal data for (S)-1e (ic19814) 83 5.1.1.6 Crystal data for (S)-[2d][Al(OC(CF3)3)4] (ic19871) 88 5.1.1.7 Crystal data for (R)-[3b][AlCl4] (ic19778) 107 5.1.1.8 Crystal data for (S)-[3d][AlCl4] (ic19728) 113 5.1.2 NMR Spectrum 117 List of Figures Figure 1. 1H NMR of the reaction of PhBCl2 and one equivalent oxazolidinone salt in CD2Cl2. 20 Figure 2. 11B NMR of the reaction of PhBCl2 and one equivalent oxazolidinone salt in CD2Cl2. 21 Figure 3. 1H NMR of MesBCl2 in CD2Cl2 (bottom), 1H NMR of the reaction of MesBCl2 and one equivalent oxazolidinone salt in CD2Cl2 (middle) and 1H NMR of the reaction of MesBCl2 and two equivalent oxazolidinone salt in CD2Cl2 (top). 22 Figure 4. 11B NMR of MesBCl2 in CD2Cl2 (bottom), 11B NMR of the reaction of MesBCl2 and one equivalent oxazolidinone salt in CD2Cl2 (middle) and 11B NMR of the reaction of MesBCl2 and two equivalent oxazolidinone salt in CD2Cl2 (top). 23 Figure 5. 1H NMR of reaction of Cp*BCl2 and one equivalent oxazolidinone salt in CD2Cl2. 24 Figure 6. Molecular structure of (R)-1a. Hydrogen atoms were omitted for clarity. 26 Figure 7. Molecular structure of (S)-1a. Hydrogen atoms were omitted for clarity. 26 Figure 8. Molecular structure of (S)-1c. Hydrogen atoms were omitted for clarity. 28 Figure 9. Molecular structure of (S)-1d. Hydrogen atoms were omitted for clarity. 29 Figure 10. Molecular structure of (S)-1e. Hydrogen atoms were omitted for clarity. 30 Figure 11. Molecular structure of (S)-chloride bridged diboron cation (S)-[2d][Al(OC(CF3)3)4]. Hydrogen atoms and counter anoin were omitted for clarity. 33 Figure 12. Molecular structure of (R)-hypercoordinate boron cation (R)-[3b][AlCl4]. Hydrogen atoms and counter anion were omitted for clarity. 35 Figure 13. Molecular structure of (S)-hypercoordinate boron cation (S)-[3d][AlCl4]. Hydrogen atoms and counter anoin were omitted for clarity. 36 Figure 14. 1H NMR of (S)-[2c][B(C6F5)4] at -78 °C in CD2Cl2 (bottom), 1H NMR of reaction of (S)-1c and one equivalent SnCl4 at -40 °C in CD2Cl2 (middle) and 1H NMR of reaction of (S)-1c and two equivalent SnCl4 at -40 °C in CD2Cl2 (top). 39 Figure 15. 119Sn NMR of (S)-[2c][SnCl5] at -78 °C in CD2Cl2 (bottom), 119Sn NMR of (S)-[2c][SnCl5]---[SnCl4] at -78 °C in CD2Cl2 (middle), 119Sn NMR of SnCl4 at -78 °C in CD2Cl2 (top). 41 Figure 16. 119Sn NMR of [nBu4N][SnCl5]---SnCl4 at -78 °C in CD2Cl2 (top), 119Sn NMR of (S)-[2c][SnCl5]---SnCl4 at -78 °C in CD2Cl2 (bottom). 41 List of Schemes Scheme 1. Asymmetric Hydrogenation of alkene. 11 Scheme 2. Asymmetric hydroboration reactions. 13 Scheme 3. Asymmetric Reduction of ketone. 13 Scheme 4. Hydrosilylation of ketone catalyzed by ferrocene-based planar-chiral borenium cation. 14 Scheme 5. Hydrogenation of imine catalyzed by carbene-stabilized borenium cation. 14 Scheme 6. Hydrosilylation of ketones catalyzed by axially chiral borane. 15 Scheme 7. Synthesis of hydride-bridged diborane dication. 15 Scheme 8. Synthesis of diborane dication with oxidative coupling. 16 Scheme 9. Synthesis of diboron diborenium. 16 Scheme 10. Asymmetric aldol reaction. 17 Scheme 11. Retrosynthesis for catalyst design. 18 Scheme 12. Over attacking result of oxazolidinone salt react with PhBCl2. 20 Scheme 13. Synthesis of (R)-1a. 26 Scheme 14. Synthesis of (R)-1b. 27 Scheme 15. Synthesis of (S)-1c. 28 Scheme 16. Synthesis of (S)-1d. 29 Scheme 17. Synthesis of (S)-1e. 30 Scheme 18. Synthesis of (S)-chloride bridged diboron cation. 31 Scheme 19. Synthesis of (R)-hypercoordinate boron cation [3b][AlCl4]. 35 Scheme 20. Synthesis of (S)-hypercoordinate boron cation (S)-[3d][AlCl4]. 36 List of Tables Table 1. Brief summary of oxazolidinone salt react with aryl-BCl2. 17 Table 2. Optimization of catalytic asymmetric Diels-Alder reaction. 35 Table 3. Checking K[B(C6F5)4] as a halophile for catalytic asymmetric Diels-Alder reaction. 38 Table 4. Cyanosilylation of benzaldehyde and hydrolysis. 40 | |
dc.language.iso | en | |
dc.title | 掌性硼陽離子: 合成、鑑定與不對稱催化反應 | zh_TW |
dc.title | Chiral Boron Cations: Synthesis, Characterization and Asymmetric Catalysis | en |
dc.type | Thesis | |
dc.date.schoolyear | 108-1 | |
dc.description.degree | 碩士 | |
dc.contributor.oralexamcommittee | 陳榮傑,張慕傑,王華冬 | |
dc.subject.keyword | 不對稱催化,噁唑烷酮,二聚體,掌性硼陽離子,五甲基茂取代基, | zh_TW |
dc.subject.keyword | asymmetric catalysis,oxazolidinone,dimer,chiral boron cation,1,2,3,4,5-pentamethylcyclopentadiene,Diels-Alder reaction., | en |
dc.relation.page | 158 | |
dc.identifier.doi | 10.6342/NTU202000661 | |
dc.rights.note | 有償授權 | |
dc.date.accepted | 2020-03-02 | |
dc.contributor.author-college | 理學院 | zh_TW |
dc.contributor.author-dept | 化學研究所 | zh_TW |
顯示於系所單位: | 化學系 |
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