第一章 以手性硫催化劑進行不對稱 [4+1] 環化反應並應用於合成吲哚類化合物之研究 第二章 設計與合成手性共價有機骨架並應用至不對稱多烯環化反應

以作者查詢圖書館館藏

、以作者查詢臺灣博碩士

、以作者查詢全國書目

、勘誤回報

、線上人數：58

、訪客IP：18.217.118.7

姓名

洪聖宸(Sheng-Chen Hung) 查詢紙本館藏

畢業系所

化學學系

論文名稱

第一章以手性硫催化劑進行不對稱 [4+1] 環化反應並應用於合成吲哚類化合物之研究第二章設計與合成手性共價有機骨架並應用至不對稱多烯環化反應
((Thiolan-2-yl)diphenylmethanol Benzyl Ether-Catalyzed Asymmetric [4+1] Cyclization and Its Application for Synthesis of Indoline Derivative. Design and Syntheses of Chiral Covalent Organic Framework and Its Application for Asymmetric Polyene Cyclization.)

檔案

[Endnote RIS 格式]

[Bibtex 格式]

[相關文章]

[文章引用]

[完整記錄]

[館藏目錄]

至系統瀏覽論文 ( 永不開放)

摘要(中)

在許多天然物和藥物中經常可以發現到五員環的結構，因此 [4+1] 環
化反應引起許多化學家研究的興趣，而如何合成出具有手性的五員環化合
物，更具有挑戰性。本論文第一章節主要目標是利用本實驗室所開發的手性硫化物與溴化芐基形成偶極體，再與起始物進行 [4+1] 環化反應。利用手性硫催化劑進行環化反應時，會因為立體障礙的因素，導致在進行加成時，會選擇立體阻礙較小的位向進行加成，進而得到具有高鏡像超越值的五員環化合物，經過許多條件的篩選與優化，但還是無法得到良好的產率與鏡像選擇性。
本論文第二章節主要目的希望能藉由第二代 Grubbs 催化劑將分別帶有烯基的手性單體與架橋分子共價聯結而形成有機骨架，並將此共價有基骨架應用在不對稱多烯環化反應。由於共價有機骨架不溶於有機溶劑的性質，可以在不對稱多烯環化反應結束後容易回收，同時也希望能達到重複使用的效果。而單體選擇聯萘酚並進行修飾，其原因為聯萘酚能與四氯化錫結合而形成路易士酸輔助手性布忍斯特酸複合體，可應用於不對稱多烯環化反應。

摘要(英)

Five-membered ring is an important structure in natural product and medicinal chemistry. Therefore, [4+1] cyclization has gained much more attention from organic chemists.
The main goal of the first chapter of in this thesis is to use the chiral tetrahydrothiophene ligand developed by our lab for the metal-catalyzed asymmetric [4+1] cyclization of propargylic carbamates and sulfur ylides. Finally, we successfully obtained the [4+1] cyclization products with up to 73% yield and 47% ee.
The main goal of second chapter is to use the 2nd generation Grubbs catalyst to crosslink the chiral monomer and linker to form a covalent organic framework (COF), which would be then applied to polyene cyclizations. The reason we choose 1,1`-Bi-2-naphtol (BINOL) as the monomer is that it can complex with Tin (IV) chloride for the formation of a Lewis acid-assisted chiral Brønsted acid system for catalyzing the asymmetric polyene cyclization. Although the COFs we obtained from the olefin cross-metathesiss successfully catalyzed the polyene cyclization, the enantioselectivity is low.

關鍵字(中)

★ 硫偶極體
★ 不對稱催化
★ [4+1] 環化反應
★ 不對稱多烯環化反應

關鍵字(英)

★ sulfur ylide
★ asymmetric catalysis
★ [4+1] cyclization
★ asymmetric polyene cyclization

論文目次

中文摘要..................................................i
英文摘要................................................iii
總目錄..................................................vii
圖目錄...................................................xi
式目錄..................................................xii
縮寫說明...............................................xvii
第一章以手性硫催化劑進行不對稱 [4+1] 環化反應並應用於合成吲哚類化合物之研究..............................................1
第一節緒論...............................................1
1-1 偶極體................................................1
1-2 五員環文獻回顧........................................5
1-3 本實驗室過去的文獻回顧................................10
1-4 研究動機.............................................15
第二節結果與討論.........................................17
2-1不對稱硫催化劑及反應起始物的合成路徑.....................17
2-2 利用銅催化劑進行 [4+1] 環化反應........................20
2-2-1 [4+1] 環化反應的溫度條件篩選........................20
2-2-2 [4+1] 環化反應的溶劑條件篩選........................22
2-2-3 [4+1] 環化反應的鹼條件篩選..........................24
2-2-4利用不同金屬催化劑進行 [4+1] 環化反應.................25
2-2-5反應機制的探討.......................................27
2-3 手性硫催化劑以催化量的方式進行 [4+1] 環化反應...........29
2-4 手性硫催化劑以卡賓的方式進行 [4+1] 環化反應.............31
第三節結論..............................................34
第二章設計與合成手性共價有機骨架並應用至不對稱多烯環化反應...35
第一節緒論..............................................35
1-1 不對稱多烯環化文獻回顧................................35
1-2 共價有機骨架.........................................44
1-3 研究動機.............................................48
第二節結果與討論.........................................53
2-1 單體與架橋分子與反應的起始物的合成......................53
2-2 合成COF的條件篩選探討................................57
2-2-1合成COF的單體及架橋分子比例的篩選並應用在不對稱多烯環化反應 ........................................................57
2-2-2 合成COF的溶劑和條件篩選並應用在不對稱多烯環化反應.....60
2-2-3 合成COF的反應時間條件篩選並應用在不對稱多烯環化反應...62
2-3 不同的單體與相同的架橋分子合成的COF並應用在不對稱多烯環化反應.......................................................65
2-4 不同的單體與不同的架橋分子合成的COF並應用在不對稱多烯環化反應.......................................................73
2-5 固態核磁共振分析......................................79
第三章結論..............................................81
第四章實驗部分...........................................82
4-1 General information................................82
4-2 Procedure and spectroscopic data...................83
第五章文獻參考.........................................120

參考文獻

1. Wittig, G.; Schöllkopf, U., Über Triphenyl‐phosphin‐methylene als olefinbildende Reagenzien (I. Mitteil. J Chemische Berichte 1954, 87 (9), 1318-1330.
2. Johnson, A. W.; LaCount, R. B., The Chemistry of Ylids. VI. Dimethylsulfonium Fluorenylide—A Synthesis of Epoxides1. J. Am. Chem. Soc. 1961, 83 (2), 417-423.
3. Corey, E.; Chaykovsky, M., Dimethyloxosulfonium methylide ((CH3) 2SOCH2) and dimethylsulfonium methylide ((CH3) 2SCH2). Formation and application to organic synthesis. J. Am. Chem. Soc. 1965, 87 (6), 1353-1364.
4. Payne, G. B., Cyclopropanes from reactions of ethyl dimethylsulfuranylideneacetate with. alpha, beta.-unsaturated compounds. J. Org. Chem. 1967, 32 (11), 3351-3355.
5. Zheng, J.-C.; Zhu, C.-Y.; Sun, X.-L.; Tang, Y.; Dai, L.-X., Highly Diastereoselective and Enantioselective Formal (4+ 1 Ylide Annulation for the Synthesis of Optically Active Dihydrofurans. J. Org. Chem 2009, 40 (3), i.
6. Li, T.-R.; Tan, F.; Lu, L.-Q.; Wei, Y.; Wang, Y.-N.; Liu, Y.-Y.; Yang, Q.-Q.; Chen, J.-R.; Shi, D.-Q.; Xiao, W.-J., Asymmetric trapping of zwitterionic intermediates by sulphur ylides in a palladium-catalysed decarboxylation-cycloaddition sequence. Nat. Commun 2014, 5 (1), 1-10.
7. Wang, Q.; Qi, X.; Lu, L. Q.; Li, T. R.; Yuan, Z. G.; Zhang, K.; Li, B. J.; Lan, Y.; Xiao, W. J., Iron‐Catalyzed Decarboxylative (4+ 1) Cycloadditions: Exploiting the Reactivity of Ambident Iron‐Stabilized Intermediates. Angew. Chem 2016, 128 (8), 2890-2894.
8. Punna, N.; Das, P.; Gouverneur, V. r.; Shibata, N., Highly diastereoselective synthesis of trifluoromethyl indolines by interceptive benzylic decarboxylative cycloaddition of nonvinyl, trifluoromethyl benzoxazinanones with sulfur ylides under palladium catalysis. Org. Lett. 2018, 20 (6), 1526-1529.
9. 黃孟婷. 手性硫化物於催化性氮丙啶化反應之應用. 國立臺灣師範大學, 2013.
10. 吳欣怡, 手性四氫噻吩配位基的合成及其應用在不對稱催化反應之研究. 國立中央大學 2012.
11. 郭昱成. 以手性有機硫催化劑進行不對稱環丙烷化反應之研究與新型手性呋喃化合物開發. 國立中正大學, 2017.
12. 鄭珮彤. 以手性有機硒催化劑進行不對稱環丙烷化反應之研究. 國立中正大學, 2020.
13. Clergue, S.; Rousseau, O.; Delaunay, T.; Dequirez, G.; Tran, T. V.; El Aakchioui, S.; Barozzino‐Consiglio, G.; Robiette, R. J. C. A. E. J., Asymmetric Sulfur‐Ylide‐Mediated Formal [4+ 1]‐Annulation Reaction: Scope and Mechanism. Chem. Eur.J.2018, 24 (44), 11417-11425.
14. 包慧彥. 以手性有機硫催化劑進行不對稱環丙烷化反應並應用於合成吡咯類化合物之研究. 國立中央大學, 2020.
15. Wang, Q.; Li, T.-R.; Lu, L.-Q.; Li, M.-M.; Zhang, K.; Xiao, W.-J., Catalytic asymmetric [4+ 1] annulation of sulfur ylides with copper–allenylidene intermediates. J. Am. Chem. Soc. 2016, 138 (27), 8360-8363.
16. Leth, L. A.; Glaus, F.; Meazza, M.; Fu, L.; Thøgersen, M. K.; Bitsch, E. A.; Jørgensen, K. A., Decarboxylative [4+ 2] cycloaddition by synergistic palladium and organocatalysis. Angew.Chem 2016, 128 (49), 15498-15502.
17. Aggarwal, V. K.; Alonso, E.; Hynd, G.; Lydon, K. M.; Palmer, M. J.; Porcelloni, M.; Studley, J. R., Catalytic asymmetric synthesis of epoxides from aldehydes using sulfur ylides with in situ generation of diazocompounds. Angew.Chem. Int.Ed. 2001, 40 (8), 1430-1433.
18. Ishihara, K.; Nakamura, S.; Yamamoto, H., The first enantioselective biomimetic cyclization of polyprenoids. J. Am. Chem. Soc. 1999, 121 (20), 4906-4907.
19. Ishibashi, H.; Ishihara, K.; Yamamoto, H., A New Artificial Cyclase for Polyprenoids: Enantioselective Total Synthesis of (−)-Chromazonarol,(+)-8-e pi-Puupehedione, and (−)-11 ‘-Deoxytaondiol Methyl Ether. J. Am. Chem. Soc. 2004, 126 (36), 11122-11123.
20. Upar, K. B.; Mishra, S. J.; Nalawade, S. P.; Singh, S. A.; Khandare, R. P.; Bhat, S. V., Efficient enantioselective synthesis of (+)-sclareolide and (+)-tetrahydroactinidiolide: chiral LBA-induced biomimetic cyclization. Tetrahedron 2009, 20 (14), 1637-1640.
21. Surendra, K.; Corey, E., Highly enantioselective proton-initiated polycyclization of polyenes. J. Am. Chem. Soc. 2012, 134 (29), 11992-11994.
22. Surendra, K.; Rajendar, G.; Corey, E., Useful catalytic enantioselective cationic double annulation reactions initiated at an internal π-bond: Method and applications. J. Am. Chem. Soc. 2014, 136 (2), 642-645.
23. Sakakura, A.; Sakuma, M.; Ishihara, K., Chiral Lewis base-assisted Brønsted acid (LBBA)-catalyzed enantioselective cyclization of 2-geranylphenols. Org. Lett. 2011, 13 (12), 3130-3133.
24. Lin, S.-C.; Chein, R.-J., Total synthesis of the labdane diterpenes galanal A and B from geraniol. J. Org. Chem 2017, 82 (3), 1575-1583.
25. Cote, A. P.; Benin, A. I.; Ockwig, N. W.; O′Keeffe, M.; Matzger, A. J.; Yaghi, O. M., Porous, crystalline, covalent organic frameworks. Science 2005, 310 (5751), 1166-1170.
26. Li, Z.; Feng, X.; Zou, Y.; Zhang, Y.; Xia, H.; Liu, X.; Mu, Y., A 2D azine-linked covalent organic framework for gas storage applications. Chem Commun. 2014, 50 (89), 13825-13828.
27. Han, X.; Zhang, J.; Huang, J.; Wu, X.; Yuan, D.; Liu, Y.; Cui, Y., Chiral induction in covalent organic frameworks. Nat. Commun. 2018, 9 (1), 1-10.
28. Zhou, D.; Tan, X.; Wu, H.; Tian, L.; Li, M., Synthesis of C− C Bonded Two‐Dimensional Conjugated Covalent Organic Framework Films by Suzuki Polymerization on a Liquid–Liquid Interface. Angew. Chem 2019, 131 (5), 1390-1395.
29. Gopalakrishnan, D.; Dichtel, W. R., Direct detection of RDX vapor using a conjugated polymer network. J. Am. Chem. Soc. 2013, 135 (22), 8357-8362.
30. Huang, M.-T.; Wu, H.-Y.; Chein, R.-J., Enantioselective synthesis of diaryl aziridines using tetrahydrothiophene-based chiral sulfides as organocatalysts. Chem. Commun. 2014, 50 (9), 1101-1103.
31. Jin, F.-Z.; Zhao, C.-C.; Ma, H.-C.; Chen, G.-J.; Dong, Y.-B., Homochiral BINAPDA-Zr-MOF for Heterogeneous Asymmetric Cyanosilylation of Aldehydes. Inorg. Chem. 2019, 58 (14), 9253-9259.
32. Endo, K.; Hamada, D.; Yakeishi, S.; Ogawa, M.; Shibata, T., Multinuclear Cu-catalysts based on SPINOL-PHOS in asymmetric conjugate addition of organozinc reagents. Org. Lett. 2012, 14 (9), 2342-2345.
33. Hong, T.; Zhang, Z.; Sun, Y.; Tao, J.-J.; Tang, J.-D.; Xie, C.; Wang, M.; Chen, F.; Xie, S.-S.; Li, S., Chiral Metallacycles as Catalysts for Asymmetric Conjugate Addition of Styrylboronic Acids to α, β-Enones. J. Am. Chem. Soc. 2020, 142 (23), 10244-10249.
34. Sellner, H.; Faber, C.; Rheiner, P. B.; Seebach, D., Immobilization of BINOL by cross‐linking copolymerization of styryl derivatives with styrene, and applications in enantioselective Ti and Al Lewis acid mediated additions of Et2Zn and Me3SiCN to aldehydes and of diphenyl nitrone to enol ethers. Chem. Eur. J. 2000, 6 (20), 3692-3705.
35. Liu, H.; Luo, Y.; Zhang, J.; Liu, M.; Dong, L., Rapid Synthesis of Alkenylated BINOL Derivatives via Rh (III)-Catalyzed C–H Bond Activation. Org. Lett. 2020, 22 (12), 4648-4652.
36. Yang, L.; Yang, F.; Lan, J.; Gao, G.; You, J.; Su, X., Rational design of BINOL-based diimidazolyl ligands: homochiral channel-like mono-component organic frameworks by hydrogen-bond-directed self-assembly. Org. Biomol. Chem 2011, 9 (8), 2618-2621.
37. Di Credico, B.; Fabrizi De Biani, F.; Gonsalvi, L.; Guerri, A.; Ienco, A.; Laschi, F.; Peruzzini, M.; Reginato, G.; Rossin, A.; Zanello, P., Cyclopentadienyl ruthenium (II) complexes with bridging alkynylphosphine ligands: Synthesis and electrochemical studies. Chem. Eur. J. 2009, 15 (44), 11985-11998.
38. Myahkostupov, M.; Castellano, F. N., Tetrahedral rigid core antenna chromophores bearing bay-substituted perylenediimides. Tetrahedron 2015, 71 (51), 9519-9527.
39. Lin, S.-C.; Chein, R.-J., Total synthesis of the labdane diterpenes galanal A and B from geraniol. J. Org. Chem 2017, 82 (3), 1575-1583.

指導教授

陳榮傑謝發坤(Rong-Jie Chein Fa-Kuen Shieh)

審核日期

2021-9-30

推文