通過鄰芳乙炔基芐醇的氫溴化 和氧異構合成 2-芳基苯乙酮

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管子萱(kuan tzu-hsuan) 查詢紙本館藏

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化學學系

論文名稱

通過鄰芳乙炔基芐醇的氫溴化和氧異構合成 2-芳基苯乙酮

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至系統瀏覽論文 (2024-9-1以後開放)

摘要(中)

三甲基溴矽烷(bromotrimethylsilane)促進鄰芳乙炔基芐醇((oarylethynyl)
benzyl)生成溴取代的2-芳基苯乙酮(brominated 2-aryl
acetophenone)，並透過追蹤1H NMR 探討了其反應機制，此方法不含
金屬且操作簡單。
利用該方法我們製備了20 種不同的衍生物，其中產率最高可達
到99%，此外，我們還嘗試做了一些應用，進一步證明了該方法的實
用性。

摘要(英)

A metal-free and operationally simple protocol has been developed to
prepare 2-Aryl acetophenone derivatives from readily available (o-
Arylethynyl)benzyl alcohols under an acid condition.
The reaction is scalable for 20 examples and the yields up to 99%,
further applications demonstrated the practicability of the protocol.

關鍵字(中)

★ 方法學

關鍵字(英)

論文目次

總目錄
中文論文摘要 .......................................................................................... i
Abstract ................................................................................................... ii
總目錄 ....................................................................................................iii
圖目錄 .................................................................................................... vi
表目錄 .................................................................................................. viii
附圖目錄 ................................................................................................ ix
第一章序論 ........................................................................................... 1
1-1 前言............................................................................................. 1
1-2 合成2-芳基苯乙酮之文獻探討 ................................................. 2
1-3 相鄰基團參與二芳基炔烴的反應 .............................................. 4
1-4 研究動機 ..................................................................................... 6
第二章結果與討論 ............................................................................... 7
2-1 優化反應條件 ............................................................................... 7
2-2 官能基效應 ................................................................................. 10
iv
2-3 推測反應機構 ............................................................................. 18
2-4 應用性反應 ................................................................................. 20
第三章通過鄰苯乙炔基芐基醚的親電加成合成異色烯 ................... 22
3-1 研究動機 ..................................................................................... 22
3-2 優化反應條件 ............................................................................. 23
3-3 官能基效應 ................................................................................. 25 第四章結合普林斯反應之串級反應 .................................................. 28
4-1 研究動機 ..................................................................................... 28
4-2 優化反應條件 ............................................................................. 29
4-3 官能基效應 ................................................................................. 30
第五章後續研究計劃 .......................................................................... 37
第六章結論 ......................................................................................... 39
第七章實驗部分 ................................................................................. 40
7-1 溶劑及處理過程 ......................................................................... 40
7-2 實驗器材與儀器 ......................................................................... 41
7-3 實驗步驟與光譜資訊 ................................................................. 43
第八章參考資料 ................................................................................. 86

參考文獻

1. Zhang, M.; Fang, X.; Neumann, H.; Beller, M., General and Regioselective Synthesis of Pyrroles via Ruthenium-Catalyzed Multicomponent Reactions. Journal of the American Chemical Society 2013, 135 (30), 11384-11388.
2. Wei, Y.; Deb, I.; Yoshikai, N., Palladium-Catalyzed Aerobic Oxidative Cyclization of N-Aryl Imines: Indole Synthesis from Anilines and Ketones. Journal of the American Chemical Society 2012, 134 (22), 9098-9101.
3. Soh, C. H.; Chui, W. K.; Lam, Y., An Efficient and Expeditious Synthesis of Di- and Monosubstituted 2-Aminoimidazoles. Journal of Combinatorial Chemistry 2008, 10 (1), 118-122.
4. Kang, P.; Foote, C. S., Photosensitized Oxidation of 13C,15N-Labeled Imidazole Derivatives. Journal of the American Chemical Society 2002, 124 (32), 9629-9638.
5. Little, T. L.; Webber, S. E., A Simple and Practical Synthesis of 2-Aminoimidazoles. The Journal
of Organic Chemistry 1994, 59 (24), 7299-7305.
6. Xi, L.-Y.; Zhang, R.-Y.; Liang, S.; Chen, S.-Y.; Yu, X.-Q., Copper-Catalyzed Aerobic Synthesis of 2-Arylpyridines from Acetophenones and 1,3-Diaminopropane. Organic Letters 2014, 16 (20), 5269-5271.
7. Shi, T.; Kaneko, L.; Sandino, M.; Busse, R.; Zhang, M.; Mason, D.; Machulis, J.; Ambrose, A. J.; Zhang, D. D.; Chapman, E., One-Step Synthesis of Thieno[2,3-d]pyrimidin-4(3H)-ones via a Catalytic Four-Component Reaction of Ketones, Ethyl Cyanoacetate, S8, and Formamide. ACS Sustainable Chemistry & Engineering 2019, 7 (1), 1524-1528.
8. Das, J.; Singh, K.; Vellakkaran, M.; Banerjee, D., Nickel-Catalyzed Hydrogen-Borrowing Strategy for α-Alkylation of Ketones with Alcohols: A New Route to Branched gem-Bis(alkyl) Ketones. Organic Letters 2018, 20 (18), 5587-5591.
9. Sithambaram, S. D., Y.; Li, W.; Shen, X.; Gaenzler, F.; Suib, S. L, Manganese octahedral molecular sieves catalyzed tandem process for synthesis of quinoxalines. Green Chem 2008, 10, 1029– 1032.
10. Dong, K.-Y.; Qin, H.-T.; Bao, X.-X.; Liu, F.; Zhu, C., Oxime-Mediated Facile Access to 5-Methylisoxazoles and Applications in the Synthesis of Valdecoxib and Oxacillin. Organic Letters 2014, 16 (20), 5266-5268.
11. Alonso, F.; Beletskaya, I. P.; Yus, M., Transition-Metal-Catalyzed Addition of Heteroatom−Hydrogen Bonds to Alkynes. Chemical Reviews 2004, 104 (6), 3079-3160.
12. Hintermann, L. L., Catalytic Hydration of Alkynes and Its Application in Synthesis. Synthesis 2007, 1121– 1150.
13. Antenucci, A. F., P.; Fornaiolo, M. V.; Di Silvio, S.; Mazzetti, S.; Mencarelli, P.; Salvio, R.; Bassetti, ron(III)-Catalyzed Hydration of Unactivated Internal Alkynes in Weak Acidic Medium, under Lewis Acid-Assisted Brønsted Acid Catalysis. Adv. Synth. Catal. 2019, 4517– 4526.
14. Hassam, M. L., W.-S, Copper-catalyzed Markovnikov hydration of alkynes. Tetrahedron 2015, 71, 2719– 2723.
15. Grotjahn, D. B.; Lev, D. A., A General Bifunctional Catalyst for the Anti-Markovnikov Hydration of Terminal Alkynes to Aldehydes Gives Enzyme-Like Rate and Selectivity Enhancements. Journal of the American Chemical Society 2004, 126 (39), 12232-12233.
16. James, B. R.; Rempel, G. L., Hydration of acetylenes catalyzed by rhodium(III) chloride complexes. Journal of the American Chemical Society 1969, 91 (4), 863-865.
17. Dubovtsev, A. Y.; Shcherbakov, N. V.; Dar’in, D. V.; Kukushkin, V. Y., Nature of the Nucleophilic Oxygenation Reagent Is Key to Acid-Free
Gold-Catalyzed Conversion of Terminal and Internal Alkynes to 1,2-Dicarbonyls. The Journal of Organic Chemistry 2020, 85 (2), 745-757.
18. Baidossi, W.; Lahav, M.; Blum, J., Hydration of Alkynes by a PtCl4−CO Catalyst. The Journal of Organic Chemistry 1997, 62 (3), 669-672.
19. Asao, N.; Nogami, T.; Takahashi, K.; Yamamoto, Y., Pd(II) Acts Simultaneously as a Lewis Acid and as a Transition-Metal Catalyst: Synthesis of Cyclic Alkenyl Ethers from Acetylenic Aldehydes. Journal of the American Chemical Society 2002, 124 (5), 764-765.
20. Dell’Acqua, M.; Castano, B.; Cecchini, C.; Pedrazzini, T.; Pirovano, V.; Rossi, E.; Caselli, A.; Abbiati, G., Mild Regiospecific Synthesis of 1-Alkoxy-isochromenes Catalyzed by Well-Defined [Silver(I)(Pyridine-Containing Ligand)] Complexes. The Journal of Organic Chemistry 2014, 79 (8), 3494-3505.
21. Zhang, C.; Wang, G.; Zhan, L.; Yang, X.; Wang, J.; Wei, Y.; Xu, S.; Shi, M.; Zhang, J., Gold(I) or Gold(III) as Real Intermediate Species in Gold-Catalyzed Cycloaddition Reactions of Enynal/Enynone? ACS Catalysis 2020, 10 (12), 6682-6690.
22. Zhang, X.; Hou, W.; Zhang-Negrerie, D.; Zhao, K.; Du, Y., Hypervalent Iodine-Mediated Intramolecular trans-Aminocarboxylation and Oxoaminocarboxylation of Alkynes: Divergent Cascade Annulations
of Isocoumarins under Metal-Free Conditions. Organic Letters 2015, 17 (21), 5252-5255.
23. Komeyama, K.; Takahashi, K.; Takaki, K., Bismuth-Catalyzed Intramolecular Carbo-oxycarbonylation of 3-Alkynyl Esters. Organic Letters 2008, 10 (22), 5119-5122.
24. Yang, C.; Zhang, X.; Zhang-Negrerie, D.; Du, Y.; Zhao, K., PhI(OCOCF3)2-Mediated Cyclization of o-(1-Alkynyl)benzamides: Metal-Free Synthesis of 3-Hydroxy-2,3-dihydroisoquinoline-1,4-dione. The Journal of Organic Chemistry 2015, 80 (10), 5320-5328.
25. Rodríguez, E.; Grayson, M. N.; Asensio, A.; Barrio, P.; Houk, K. N.; Fustero, S., Chiral Brønsted Acid-Catalyzed Asymmetric Allyl(propargyl)boration Reaction of ortho-Alkynyl Benzaldehydes: Synthetic Applications and Factors Governing the Enantioselectivity. ACS Catalysis 2016, 6 (4), 2506-2514.
26. Padwa, A.; Krumpe, K. E.; Weingarten, M. D., An Unusual Example of a 6-Endo-Dig Addition to an Unactivated Carbon-Carbon Triple Bond. The Journal of Organic Chemistry 1995, 60 (17), 5595-5603.
27. Kotipalli, T.; Hou, D.-R., Synthesis of 3-Bromoindenes from 4-Alkynyl Alcohols/Sulfonamides and Aldehydes via Prins Cyclization, Ring-Opening and Friedel-Crafts Reactions. Asian Journal of Organic Chemistry 2019, 8 (8), 1561-1571.
28. Long, P.-W. B., X.-F.; Ye, F.; Li, L.; Xu, Z.; Yang, K.-F.; Cui, Y.-M.; Zheng, Z.-J.; Xu, L.-W, Construction of Six-Membered Silacyclic Skeletons via Platinum-Catalyzed Tandem Hydrosilylation/Cyclization with Dihydrosilanes. Adv. Synth. Catal. 2018, 360, 2825– 2830.
29. Qiu, Y.-F.; Niu, Y.-J.; Wei, X.; Cao, B.-Q.; Wang, X.-C.; Quan, Z.-J., AgSCF3/Na2S2O8-Promoted Trifluoromethylthiolation/Cyclization of o-Propargyl Arylazides/o-Alkynyl Benzylazides: Synthesis of SCF3-Substituted Quinolines and Isoquinolines. The Journal of Organic Chemistry 2019, 84 (7), 4165-4178.
30. Mancuso, R.; Mehta, S.; Gabriele, B.; Salerno, G.; Jenks, W. S.; Larock, R. C., A Simple and Mild Synthesis of 1H-Isochromenes and (Z)-1-Alkylidene-1,3-dihydroisobenzofurans by the Iodocyclization of 2-(1-Alkynyl)benzylic Alcohols. The Journal of Organic Chemistry 2010, 75 (3), 897-901.
31. Sashida, H. O., K.; Minoura, M, Studies on tellurium-containing heterocycles. Part 18.1 Preparation and structure of 2-benzotelluropyrylium salts and 2-benzoselenopyrylium salts. J. Chem. Soc 2002, 606– 612.
32. Jongcharoenkamol, J.; Chuathong, P.; Amako, Y.; Kono, M.; Poonswat, K.; Ruchirawat, S.; Ploypradith, P., Selective Divergent Synthesis of Indanols, Indanones, and Indenes via Acid-Mediated
Cyclization of (Z)- and (E)-(2-Stilbenyl)methanols and Its Application for the Synthesis of Paucifloral F Derivatives. The Journal of Organic Chemistry 2018, 83 (21), 13184-13210.
33. Hessler, F. B., R.; Kadlčíková, A.; Belle, R.; Kotora, M., Enantioselective Allylation of Selected ortho-Substituted Benzaldehydes: A Comparative Study. Eur. J. Org. Chem 2014.
34. Li, D. Y.; Shi, K. J.; Mao, X. F.; Chen, G. R.; Liu, P. N., Transition Metal-Free Cascade Reactions of Alkynols to Afford Isoquinolin-1(2H)-one and Dihydroisobenzofuran Derivatives. The Journal of Organic Chemistry 2014, 79 (10), 4602-4614.
35. Ackermann, M.; Bucher, J.; Rappold, M.; Graf, K.; Rominger, F.; Hashmi, A. S. K., [3,3]-Sigmatropic Rearrangement Step in the Gold-Catalyzed Cyclization of Allyl-(ortho-alkinylphenyl)methyl Ethers. Chemistry – An Asian Journal 2013, 8 (8), 1786-1794.
36. Zhu, S.; Huang, H.; Zhang, Z.; Ma, T.; Jiang, H., Mechanistic Insight into Transition Metal-Catalyzed Reaction of Enynal/Enynone with Alkenes: Metal-Dependent Reaction Pathway. The Journal of Organic Chemistry 2014, 79 (13), 6113-6122.
37. Mehta, S.; Waldo, J. P.; Larock, R. C., Competition Studies in Alkyne Electrophilic Cyclization Reactions. The Journal of Organic Chemistry 2009, 74 (3), 1141-1147.
38. Mariaule, G.; Newsome, G.; Toullec, P. Y.; Belmont, P.; Michelet, V., Silver-Catalyzed Domino Hydroarylation/Cycloisomerization Reactions of ortho-Alkynylbenzaldehydes: An Entry to Functionalized Isochromene Derivatives. Organic Letters 2014, 16 (17), 4570-4573.
39. Hsieh, H.-Y.; Lee, W.-C.; Senadi, G. C.; Hu, W.-P.; Liang, J.-J.; Tsai, T.-R.; Chou, Y.-W.; Kuo, K.-K.; Chen, C.-Y.; Wang, J.-J., Discovery, Synthetic Methodology, and Biological Evaluation for Antiphotoaging Activity of Bicyclic[1,2,3]triazoles: In Vitro and in Vivo Studies. Journal of Medicinal Chemistry 2013, 56 (13), 5422-5435.
40. Costello, J. P.; Ferreira, E. M., Regioselectivity Influences in Platinum-Catalyzed Intramolecular Alkyne O–H and N–H Additions. Organic Letters 2019, 21 (24), 9934-9939.
41. Fyfe, T. J.; Kellam, B.; Sykes, D. A.; Capuano, B.; Scammells, P. J.; Lane, J. R.; Charlton, S. J.; Mistry, S. N., Structure–Kinetic Profiling of Haloperidol Analogues at the Human Dopamine D2 Receptor. Journal of Medicinal Chemistry 2019, 62 (21), 9488-9520.
42. Ueda, T.; Kanomata, N.; Machida, H., Synthesis of Planar-Chiral Paracyclophanes via Samarium(II)-Catalyzed Intramolecular Pinacol Coupling. Organic Letters 2005, 7 (12), 2365-2368.
43. Nicolaou, K. C.; Reingruber, R.; Sarlah, D.; Bräse, S., Enantioselective Intramolecular Friedel−Crafts-Type α-Arylation of Aldehydes. Journal of the American Chemical Society 2009, 131 (6), 2086-2087.
44. Shan, G.; Flegel, J.; Li, H.; Merten, C.; Ziegler, S.; Antonchick, A. P.; Waldmann, H., C−H Bond Activation for the Synthesis of Heterocyclic Atropisomers Yields Hedgehog Pathway Inhibitors. Angewandte Chemie International Edition 2018, 57 (43), 14250-14

指導教授

侯敦仁

審核日期

2021-8-30

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