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

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吳欣怡(Hsin-Yi Wu) 查詢紙本館藏

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化學學系

論文名稱

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
(Studies of Chiral Tetrahydrothiophenes in Asymmetric Catalysis)

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摘要(中)

四氫噻吩衍生物 (S)-diphenyl(tetrahydrothiophen-2-yl)methanol (1) 的合成是以市售5-溴戊酸為起始物，經由五步的合成路徑而得。除此之外，我們將探討 (S)-(1) 於不對稱催化領域的應用，如：不對稱環氧化反應、不對稱烯丙基取代反應。在不對稱環氧化的應用上，最佳可以得到反式產物 (34) 92 % e.e；而不對稱烯丙基烷化卅醚化的應用上，仍有改善的空間。

摘要(英)

A novel chiral tetrahydrothiophene derivative (1) was obtained enantioselectively from commercially available 5-bromopentanoic acid through a 5- step synthetic route. We also demostrated the applications of this chiral ligand in asymmetric sulfur ylide epoxidation and organometallic asymmetric allylic substitution.

關鍵字(中)

★ 不對稱催化
★ 四氫噻吩配位基

關鍵字(英)

★ Asymmetric Catalysis
★ Tetrahydrothiophenes

論文目次

中文摘要 i
ABSTRACT ii
目錄　Table of Contents iii
圖目錄　List of Figures v
表目錄　List of Tables viii
縮寫列表　List of Abbreviations ix
第一章　緒論 1
1-1　配位基 diphenyl(tetrahydrothiophen-2-yl)methanol (1) 簡介 1
1-1-1　(R)-diphenyl(tetrahydrothiophen-2-yl)methanol (1) 合成路徑 1
1-1-2　(S)-diphenyl(tetrahydrothiophen-2-yl)methanol (1) 合成路徑 2
1-1-3　以苯甲醛為起始物進行不對稱烷基化催化反應 3
1-2　環氧化反應 (epoxidation) 5
1-2-1　以硫化物作為催化劑進行環氧化反應 (Sulfide-catalyzed epoxidations) 6
1-2-2　以硫化物催化不對稱環氧化反應 6
1-2-3　天然物合成之應用 9
1-3　過渡金屬催化不對稱烯丙基烷化反應 10
1-3-2 釕金屬錯合物催化不對稱烯丙基反應 12
第二章　結果與討論 14
2-1　配位基 (ligand) (S)-(1) 的合成 14
2-1-1　逆合成分析 15
2-1-2　配位基 (S)-(1) 的製備 16
2-2　不對稱硫化物催化環氧化反應之應用 22
2-2-1　將配位基 (1) 應用於不對稱環氧化反應 22
2-2-2　製備配位基 (S)-2-(methoxydiphenylmethyl)tetrahydrothiophene (20) 27
2-2-3　製備配位基 (S)-(diphenyl(tetrahydrothiophen-2-yl)methoxy) trimethylsilane (21) 27
2-2-4　製備配位基 (S)-2-((benzyloxy)diphenylmethyl)tetrahydrothiophene (22) 28
2-2-5　製備配位基 (S)-2-(isopropoxydiphenylmethyl)tetrahydrothiophene (42) 28
2-2-6　製備配位基 (S)-2-(phenoxydiphenylmethyl)tetrahydrothiophene (43) 29
2-3　配位基 (1) 於有機金屬不對稱催化反應上的應用 30
2-3-1　銅錯合物行不對稱烷化反應之選擇性初步研究 30
2-3-2　鈀錯合物進行不對稱烷化卅醚化反應之選擇性初步研究 33
2-3-3　製備可能的錯合物 (58) 及 (60) 34
2-3-4　釕錯合物行不對稱醚化及烷化反應之選擇性初步研究 36
2-3-5　製備配位基 (S)-(diphenyl(tetrahydrothiophen-2-yl)methoxy)　diisopropylphosphine (49) 39
2-3-6　製備配位基 (S)-(diphenyl(tetrahydrothiophen-2-yl)methoxy) diphenylphosphine (50) 40
第三章　結論 41
第四章　實驗及光譜數據 42
4-1　實驗儀器 42
4-2　實驗步驟及光譜數據 44
第五章　參考文獻 69
附錄　Appendixes 77
X-ray crystallographic data of (S)-(1) 78
HPLC analysis 85
1H, 13C and 31P NMR Spectra 91

參考文獻

1. Yang, H.; Carter, R. G., Proline Sulfonamide-Based Organocatalysis: Better Late than Never. Synlett 2010, (19), 2827-2838.
2. Corey, E. J., Enantioselective Catalysis Based on Cationic Oxazaborolidines. Angew. Chem. Int. Ed. 2009, 48 (12), 2100-2117.
3. Corey, E. J.; Helal, C. J., Reduction of Carbonyl Compounds with Chiral Oxazaborolidine Catalysts: A New Paradigm for Enantioselective Catalysis and a Powerful New Synthetic Method. Angew. Chem. Int. Ed. 1998, 37 (15), 1986-2012.
4. Dalko, P. I.; Moisan, L., In the Golden Age of Organocatalysis. Angew. Chem. Int. Ed. 2004, 43 (39), 5138-5175.
5. List, B., Proline-catalyzed asymmetric reactions. Tetrahedron 2002, 58 (28), 5573-5590.
6. Shiina, I. K., Katsuhiko; Kuramoto, Yu-suke Enantioselective Alkylation of Aldehydes with Diethylzinc Using a New Catalyst System, ((R)-Thiolan-2-yl) diphenylmethanol and Metal Alkoxides. Chem. Lett. 2002, 164-165.
7. Wrobel, J. T.; Hejchman, E., Spiro Derivatives of Tetrahydrothiophene- Synthesis of the Quinolizidine (3-Spiro-2’’)Tetrahydrothiophene System Using Solid Liquid or Liquid Liquid Phase-Transfer Catalysis. Synthesis 1987, (5), 452-455.
8. Claeson, G. J., Hans G. , Resolution and configuration of thiophane-2- carboxylic acid. Arkiv för kemi. 1966, 26, 247-257.
9. Chein, R. J., unpublished result.
10. Johnson, A. W. L., R. B., 9-Dimethylsulfonium fluorenylide. Chem. Ind. (London) 1958, 1440.
11. Corey, E. J.; 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.
12. Gololobov, Y. G.; Nesmeyanov, A. N.; lysenko, V. P.; Boldeskul, I. E., Twenty-five years of dimethylsulfoxonium ethylide (corey’’s reagent). Tetrahedron 1987, 43 (12), 2609-2651.
13. Furukawa, N.; Okano, K.; Fujihara, H., Synthesis of Oxiranes by Using Sulfides-Sulfonium Salts as Mediators. Nippon Kagaku Kaishi 1987, (7), 1353-1358.
14. Furukawa, N.; Sugihara, Y.; Fujihara, H., Camphoryl sulfide as a chiral auxiliary and a mediator for one-step synthesis of optically active 1,2-diaryloxiranes. J. Org. Chem. 1989, 54 (17), 4222-4224.
15. Li, A.-H.; Dai, L.-X.; Hou, X.-L.; Huang, Y.-Z.; Li, F.-W., Preparation of Enantiomerically Enriched (2R,3R)- or (2S,3S)-trans-2,3-Diaryloxiranes via Camphor-Derived Sulfonium Ylides. J. Org. Chem. 1996, 61 (2), 489-493.
16. Julienne, K.; Metzner, P.; Henryon, V.; Greiner, A., A Simple C2 Symmetrical Sulfide for a One-Pot Asymmetric Conversion of Aldehydes into Oxiranes. J. Org. Chem. 1998, 63 (13), 4532-4534.
17. Zanardi, J.; Leriverend, C.; Aubert, D.; Julienne, K.; Metzner, P., A Catalytic Cycle for the Asymmetric Synthesis of Epoxides Using Sulfur Ylides. J. Org. Chem. 2001, 66 (16), 5620-5623.
18. Saito, T.; Akiba, D.; Sakairi, M.; Kanazawa, S., Preparation of a novel, camphor-derived sulfide and its evaluation as a chiral auxiliary mediator in asymmetric epoxidation via the Corey–Chaykovsky reaction. Tetrahedron Lett. 2001, 42 (1), 57-59.
19. Winn, C. L.; Bellenie, B. R.; Goodman, J. M., A highly enantioselective one-pot sulfur ylide epoxidation reaction. Tetrahedron Lett. 2002, 43 (31), 5427-5430.
20. Miyake, Y.; Oyamada, A.; Nishibayashi, Y.; Uemura, S., Asymmetric synthesis of epoxides from aromatic aldehydes and benzyl halides catalyzed by C2 symmetric optically active sulfides having a binaphthyl skeleton. Heteroat. Chem 2002, 13 (3), 270-275.
21. Ishizaki, M.; Hoshino, O., Synthesis of novel C-2-symmetrical chiral sulfides and their utility in asymmetric epoxidation of aldehydes. Chirality 2003, 15 (4), 300-305.
22. Davoust, M.; Brière, J.-F.; Jaffrès, P.-A.; Metzner, P., Design of Sulfides with a Locked Conformation as Promoters of Catalytic and Asymmetric Sulfonium Ylide Epoxidation. J. Org. Chem. 2005, 70 (10), 4166-4169.
23. Zanardi, J.; Reboul, V.; Metzner, P., Direct utilization of naturally occurring sulfides for the asymmetric epoxidation of aldehydes mediated by catalytic ylides. Bull. Korean Chem. Soc. 2004, 25 (11), 1695-1698.
24. Minière, S.; Reboul, V.; Metzner, P.; Fochi, M.; Bonini, B. F., Catalytic ferrocenyl sulfides for the asymmetric transformation of aldehydes into epoxides. Tetrahedron: Asymmetry 2004, 15 (20), 3275-3280.
25. Hansch, M.; Illa, O.; McGarrigle, E. M.; Aggarwal, V. K., Synthesis and Application of Easily Recyclable Thiomorpholines for Use in Sulfur Ylide Mediated Asymmetric Epoxidation of Aldehydes. Chem. Asian J. 2008, 3 (8-9), 1657-1663.
26. Hayakawa, R.; Shimizu, M., Synthesis of chiral epoxides from aldehydes using sulfur ylide derived from reduced product of bakers’’ yeast reduction. Synlett 1999, (8), 1328-1330.
27. McGarrigle, E. M.; Myers, E. L.; Illa, O.; Shaw, M. A.; Riches, S. L.; Aggarwal, V. K., Chalcogenides as Organocatalysts. Chem. Rev. 2007, 107 (12), 5841-5883.
28. Illa, O.; Arshad, M.; Ros, A.; McGarrigle, E. M.; Aggarwal, V. K., Practical and Highly Selective Sulfur Ylide Mediated Asymmetric Epoxidations and Aziridinations Using an Inexpensive, Readily Available Chiral Sulfide. Applications to the Synthesis of Quinine and Quinidine. J. Am. Chem. Soc. 2010, 132 (6), 1828-1830.
29. Tsuji, J.; Takahashi, H.; Morikawa, M., Organic synthesis by means of noble metal compounds XVII. Reaction of pi-allylpalladium chloride with nucleophiles. Tetrahedron Lett. 1965, 6 (49), 4387-4388.
30. Trost, B. M.; Dietsch, T. J., New synthetic reactions. Asymmetric induction in allylic alkylations. J. Am. Chem. Soc. 1973, 95 (24), 8200-8201.
31. Trost, B. M.; Crawley, M. L., Asymmetric Transition-Metal-Catalyzed Allylic Alkylations: Applications in Total Synthesis. Chem. Rev. 2003, 103 (8), 2921-2944.
32. Evans, D. A.; Campos, K. R.; Tedrow, J. S.; Michael, F. E.; Gagné, M. R., Application of Chiral Mixed Phosphorus/Sulfur Ligands to Palladium-Catalyzed Allylic Substitutions. J. Am. Chem. Soc. 2000, 122 (33), 7905-7920.
33. Trost, B. M.; Frederiksen, M. U.; Rudd, M. T., Ruthenium-catalyzed reactions - A treasure trove of atom-economic transformations. Angew. Chem. Int. Ed. 2005, 44 (41), 6630-6666.
34. Minami, I.; Shimizu, I.; Tsuji, J., Reactions of Allylic Carbonates Catalyzed by Palladium, Rhodium, Ruthenium, Molybdenum, and Nickel-Complexes - Allylation of Carbonucleophiles and Decarboxylation-Dehydrogenation. J. Organomet. Chem. 1985, 296 (1-2), 269-280.
35. Bruneau, C.; Renaud, J. L.; Demerseman, B., Pentamethylcyclopentadienyl- ruthenium catalysts for regio- and enantioselective allylation of nucleophiles. Chem. Eur. J. 2006, 12 (20), 5178-5187.
36. Trost, B. M.; Fraisse, P. L.; Ball, Z. T., A Stereospecific Ruthenium-Catalyzed Allylic Alkylation. Angew. Chem. Int. Ed. 2002, 41 (6), 1059-1061.
37. Mbaye, M. D.; Demerseman, B.; Renaud, J. L.; Toupet, L.; Bruneau, C., Ruthenium-catalyzed O-allylation of phenols from allylic chlorides via cationic [Cp*(eta(3)-allyl)(MeCN)RuX][PF6] complexes. Adv. Synth. Catal. 2004, 346 (7), 835-841.
38. Gurbuz, N.; Ozdemir, I.; Cetinkaya, B.; Renaud, J. L.; Demerseman, B.; Bruneau, C., Regioselective allylic alkylation and etherification catalyzed by in situ generated N-heterocyclic carbene ruthenium complexes. Tetrahedron Lett. 2006, 47 (4), 535-538.
39. Mbaye, M. D.; Renaud, J. L.; Demerseman, B.; Bruneau, C., First enantioselective allylic etherification with phenols catalyzed by chiral ruthenium bisoxazoline complexes. Chem. Commun. 2004, (16), 1870-1871.
40. Kulkarni, S. S.; Newman, A. H., Design and synthesis of novel heterobiaryl amides as metabotropic glutamate receptor subtype 5 antagonists. Bioorg. Med. Chem. Lett. 2007, 17 (7), 2074-2079.
41. Wang, Z.-X.; Tu, Y.; Frohn, M.; Zhang, J.-R.; Shi, Y., An Efficient Catalytic Asymmetric Epoxidation Method. J. Am. Chem. Soc. 1997, 119 (46), 11224-11235.
42. Wong, O. A.; Shi, Y., Organocatalytic Oxidation. Asymmetric Epoxidation of Olefins Catalyzed by Chiral Ketones and Iminium Salts. Chem. Rev. 2008, 108 (9), 3958-3987.
43. Frohn, M.; Shi, Y., Chiral ketone-catalyzed asymmetric epoxidation of olefins. Synthesis 2000, (14), 1979-2000.
44. Hughes, D. L.; Reamer, R. A.; Bergan, J. J.; Grabowski, E. J. J., A mechanistic study of the Mitsunobu esterification reaction. J. Am. Chem. Soc. 1988, 110 (19), 6487-6491.
45. Lepore, S. D.; He, Y., Use of Sonication for the Coupling of Sterically Hindered Substrates in the Phenolic Mitsunobu Reaction. J. Org. Chem. 2003, 68 (21), 8261-8263.
46. Noyori, R.; Murata, S.; Suzuki, M., Trimethysilyl triflate in organic synthesis. Tetrahedron 1981, 37 (23), 3899-3910.
47. Murata, S.; Noyori, R., A facile procedure for o-tritylation. Tetrahedron Lett. 1981, 22 (22), 2107-2108.
48. Goux, C.; Massacret, M.; Lhoste, P.; Sinou, D., Stereo- and Regioselectivity in Palladium-Catalyzed Allylic Etherification. Organometallics 1995, 14 (10), 4585-4593.
49. Evans, P. A.; Leahy, D. K., Regio- and Enantiospecific Rhodium-Catalyzed Allylic Etherification Reactions Using Copper(I) Alkoxides: Influence of the Copper Halide Salt on Selectivity. J. Am. Chem. Soc. 2002, 124 (27), 7882-7883.
50. Jensen, S. B.; Rodger, S. J.; Spicer, M. D., Facile preparation of η6-p-cymene ruthenium diphosphine complexes. Crystal structure of [(η6-p-cymene)Ru (dppf)Cl]PF6. J. Organomet. Chem. 1998, 556 (1–2), 151-158.
51. Sun, Y.; Machala, M. L.; Castellano, F. N., Controlled microwave synthesis of RuII synthons and chromophores relevant to solar energy conversion. Inorg. Chim. Acta 2010, 363 (1), 283-287.
52. Mercier, A.; Yeo, W. C.; Chou, J. Y.; Chaudhuri, P. D.; Bernardinelli, G.; Kundig, E. P., Synthesis of highly enantiomerically enriched planar chiral ruthenium complexes via Pd-catalysed asymmetric hydrogenolysis. Chem. Commun. 2009, (35), 5227-5229.
53. Kündig, E. P.; Monnier, F. R., Efficient Synthesis of Tris(acetonitrile)- (η5-cyclopentadienyl)-ruthenium(II) Hexafluorophosphate via Ruthenocene. Adv. Synth. Catal. 2004, 346 (8), 901-904.
54. Chaplin, A. B.; Dyson, P. J., Catalytic Activity of Bis-phosphine Ruthenium(II)-Arene Compounds: Structure-Activity Correlations. Organometallics 2007, 26 (9), 2447-2455.
55. Srinivasan, R.; Uttamchandani, M.; Yao, S. Q., Rapid Assembly and in Situ Screening of Bidentate Inhibitors of Protein Tyrosine Phosphatases. Org. Lett. 2006, 8 (4), 713-716.
56. Robiette, R.; Conza, M.; Aggarwal, V. K., Delineation of the factors governing reactivity and selectivity in epoxide formation from ammonium ylides and aldehydes. Org. Biomol. Chem. 2006, 4 (4), 621-623.
57. Imuta, M.; Ziffer, H., Synthesis and physical properties of a series of optically active substituted trans-stilbene oxides. J. Org. Chem. 1979, 44 (14), 2505-2509.
58. Linde, C.; Koliaï, N.; Norrby, P.-O.; Åkermark, B., Experimental Evidence for Multiple Oxidation Pathways in the (salen)Mn-Catalyzed Epoxidation of Alkenes. Chem. Eur. J. 2002, 8 (11), 2568-2573.
59. Latham, C. M.; Blake, A. J.; Lewis, W.; Lawrence, M.; Woodward, S., Short Synthesis of Chiral 4-Substituted (S)-Imidazolinium Salts Bearing Sulfonates and Their Use in γ-Selective Reactions of Allylic Halides with Grignard Reagents. Eur. J. Org. Chem. 2012, 2012 (4), 699-707.
60. Jackowski, O.; Alexakis, A., Copper-Free Asymmetric Allylic Alkylation with Grignard Reagents. Angew. Chem. Int. Ed. 2010, 49 (19), 3346-3350.
61. Levy, J.-N.; Latham, C. M.; Roisin, L.; Kandziora, N.; Fruscia, P. D.; White, A. J. P.; Woodward, S.; Fuchter, M. J., The design and synthesis of novel IBiox N-heterocyclic carbene ligands derived from substituted amino-indanols. Org. Biomol. Chem. 2012, 10 (3), 512-515.
62. Yuan, F. Q.; Gao, L. X.; Han, F. S., PdCl2-catalyzed efficient allylation and benzylation of heteroarenes under ligand, base/acid, and additive-free conditions. Chem. Commun. 2011, 47 (18), 5289-5291.
63. Onitsuka, K.; Okuda, H.; Sasai, H., Regio- and Enantioselective O-Allylation of Phenol and Alcohol Catalyzed by a Planar-Chiral Cyclopentadienyl Ruthenium Complex. Angew. Chem. Int. Ed. 2008, 47 (8), 1454-1457.
64. Shang, X. J.; Xiong, Y.; Zhang, Y. X.; Zhang, L.; Liu, Z. Q., Pd(II)-Catalyzed Direct Olefination of Arenes with Allylic Esters and Ethers. Synlett 2012, (2), 259-262.

指導教授

陳榮傑(Rong-Jie Chein)

審核日期

2012-8-28

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