博碩士論文 110223037 詳細資訊




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姓名 蕭羽汶(Yu-Wen Hsiao)  查詢紙本館藏   畢業系所 化學學系
論文名稱 含氮雜環碳烯葉立德膦配位基之合成與其金催 化劑的應用
(Synthesis of N-heterocyclic carbene ylide phosphine ligands and their application in gold catalysis)
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摘要(中) 本實驗室主要研究以兩對卡賓配位基穩定中心碳的同碳雙碳烯 (carbodicarbene, CDC) 及其衍生物的反應性和配位性質。卡賓能夠提供強  供給能力,也因碳上具備空軌域因此亦有 π 電子接受能力。我們將卡賓 的性質應用於膦化學之中,藉此延伸配位基的種類以及應用性。
葉立德膦配位基 (YPhos) 為 Gessner 教授近期研究中發表的新一類膦配位基,其應用在金和鈀催化中,表現出顯著的反應活性。眾多深入的研究 表明了YPhos的特殊性來自膦葉立德 (phosphoniumylide)的強推電子能力, 但適用之葉立德化合物仍然僅限於亞烷基膦化物。含氮雜環碳烯 (NHC)為 相似於膦之常用配位基,含氮雜環烯烴膦配位基首先被 Beller 教授應用而 後被 Rivard 教授單獨分離出來,其電子性質有別於電荷分離的葉立德膦, 更傾向以烯烴的共振形式。本論文我們成功合成了含氮雜環碳烯葉立德膦 (Carbene ylide phosphine, CYPhos),借助結構中的強拉電子取代基,使得烯 烴結構更能趨近極化的兩性離子。以理論計算 (NBOanalysis)和晶體結構, 證實 CYPhos 性質更接近葉立德,並透過 Tolman 電子參數 (TEP) 和掩埋 體積 (%Vbur)描述新型配位基的電子性質以及立體效應。此外,借助理論計 算 (NCI index)以及核磁共振光譜數據得知 CYPhos 具備 secondary interaction,但因其彈性 (flexible)的性質,使得 CYPhos 反應性異於 Buchwald-type 配位基,從金(I)催化的炔類氫氨化反應和炔丙基醯胺的環化 反應證實了這一觀察結果。
摘要(英) The main research interest in our group is the synthesis and application of diversified carbodicarbene: a divalent carbon(0) species ligated by two flanking carbene ligands. The importance of using carbene moieties to provide sufficient sigma donating strength and pi accepting ability in stabilizing active species inspires us a new project of application in phosphine chemistry.
In very recent works by Gessner and co-workers, ylide-substituted phosphines (YPhos) were introduced as a new class of phosphine ligands which exhibited remarkable reactivity in gold and palladium catalysis. Aside from the growingly important YPhos ligands, using a carbene-olefin as the analog of phosphonium ylide, however, is less studied. The first N-heterocyclic olefin phosphine (NHOP) ligand was applied in palladium-catalyzed coupling reactions by Beller and later the free ligand was isolated and studied by Rivard. Inspired by the efficient YPhos gold(I) catalysis, we synthesized the variation of NHOP with an electron-withdrawing -SO2 group. According to NBO analysis and X-ray crystallography, the new ligand presents the charge-separated, zwitterionic form instead of the neutral olefin form so it is better to describe as carbene ylide phosphine (CYPhos). Tolman electronic parameter (TEP) and the buried volume (%Vbur) was calculated to determine donor strength and steric profile of CYPhos. In addition, NCI index and NMR experiments discovered that the ligand backbone of CYPhos has weak secondary interaction with Au. The smaller average buried volume as well as the flexible characteristic of CYPhos makes it less like a Buchwald-type phosphine. This observation was confirmed by testing the gold(I)- catalyzed hydroamination and cycloisomerization.
關鍵字(中) ★ 含氮雜環碳烯
★ 葉立德膦配位基
★ 含氮雜環碳烯葉立德膦
★ 金(I)催化反應
★ 炔類氫氨化反應
★ 炔丙基醯胺的環化 反應
關鍵字(英)
論文目次 摘 要 ...................................................................................................... i
ABSTRACT ..................................................................................................ii
誌謝 ..............................................................................................................iii
目錄 .............................................................................................................. iv
圖目錄 .......................................................................................................... vi
式目錄 .......................................................................................................... ix
表目錄 .......................................................................................................... xi
附圖目錄 ..................................................................................................... xii
附表目錄 ...................................................................................................xvii
符號說明 ..................................................................................................xviii
一、 緒論.....................................................................................................1
1-1 前言 ................................................................................................. 1
1-2 膦化物 ............................................................................................. 2
1-3 亞烷基磷化物 (Phosphorus ylides) ............................................... 8
1-4 碳烯 (Carbene) ............................................................................. 12
1-5 含氮雜環烯烴 (N-heterocyclic olefins, NHO) ............................ 16
1-6 含氮雜環烯烴膦配位基 (N-heterocyclic olefin phosphine, NHOP) 18
1-7 卡本 carbone ................................................................................ 20
1-8 研究動機 ....................................................................................... 25
二、 結果與討論.......................................................................................27
2-1 含氮雜環之膦配位基的合成步驟 ............................................... 27
2-2 含氮雜環膦配位基的金屬錯合物之合成步驟 ........................... 36
iv
2-2-1 含氮雜環膦配位基的金(I)金屬錯合物之合成步驟................36 2-2-2 含氮雜環膦配位基的銠(I)金屬錯合物之合成步驟................38 2-2-3 含氮雜環膦配位基的鈀(II)金屬錯合物之合成步驟..............39
2-3 含氮雜環膦配位基及其金屬錯合物之結構鑑定 ....................... 41
2-4 含氮雜環膦配位基和其金錯合物之數據分析 ........................... 53
2-4-1 含氮雜環膦配位基和其金(I)錯合物之NMR光譜分析.........53 2-4-2 含氮雜環膦配位基和其金錯合物之晶體結構分析................57
2-4-3 含氮雜環膦配位基的金(I)和鈀(II)錯合物之立體障礙空間分析 59 2-4-4 含氮雜環膦配位基的金(I)錯合物之電子性質........................62 2-4-5 含氮雜環膦配位基與其金(I)錯合物之理論計算分析............63
2-5 含氮雜環膦配位基之金(I)錯合物催化能力 ............................... 66 三、 結論...................................................................................................71
四、 實驗方法...........................................................................................72
4-1 實驗儀器 ....................................................................................... 72
4-1-1 核磁共振儀 (Nuclear magnetic resonance spectrometer) ........ 72
4-1-2X-ray單晶繞射解析 (X-raydiffractometer).............................73
4-1-3 解 析 度 磁 場 質 譜 儀 (High resolution magnetic sector mass spectrometer) ................................................................................. 73
4-2 藥品與溶劑 ................................................................................... 74
4-3 合成步驟 ....................................................................................... 75
4-4 催化反應步驟 ............................................................................. 102
4-4-1 炔類氫氨化反應的實驗步驟..................................................102
4-4-2 環異構化反應之實驗步驟......................................................103
參考文獻 ................................................................................................... 105
附錄 1 X-ray 晶體與數據......................................................................... 111
附錄 2 化合物光譜..................................................................................134
參考文獻 1. Chatt, J.; Mann, F. G., 366. The Constitution of Complex Metallic Salts. Part VIII. The Bridged Thio-Derivatives of Palladous Halides with Tertiary Phosphines. J. Am. Chem. Soc. (Resumed) 1938, (0), 1949-1954.
2. Tolman, C. A., Steric Effects of Phosphorus Ligands in Organometallic Chemistry and Homogeneous Catalysis. Chem. Rev. 1977, 77 (3), 313-348.
3. Tonner, R.; Frenking, G., Tolman’s Electronic Parameters for Divalent Carbon (0) Compounds. Organometallics 2009, 28 (13), 3901-3905.
4. Serron, S.; Huang, J.; Nolan, S., Organometallics 1998, 17, 534-539.
5. Chen, L.; Ren, P.; Carrow, B. P., Tri(1-adamantyl)phosphine: Expanding the Boundary of Electron-Releasing Character Available to Organophosphorus Compounds. J. Am.
Chem. Soc. 2016, 138 (20), 6392-6395.
6. Tolman, C. A., Phosphorus Ligand Exchange Equilibriums on Zerovalent Nickel:
Dominant Role for Steric Effects. J. Am. Chem. Soc. 1970, 92 (10), 2956-2965.
7. Dalal, M., A Textbook of Physical Chemistry–Volume 1. Dalal Institute: 2018.
8. Poater, A.; Cosenza, B.; Correa, A.; Giudice, S.; Ragone, F.; Scarano, V.; Cavallo, L., SambVca: A Web Application for the Calculation of the Buried Volume of N-
Heterocyclic Carbene Ligands. Eur. J. Inorg. Chem. 2009, 2009 (13), 1759-1766.
9. Martin, R.; Buchwald, S. L., Palladium-Catalyzed Suzuki−Miyaura Cross-Coupling Reactions Employing Dialkylbiaryl Phosphine Ligands. Acc. Chem. Res. 2008, 41 (11), 1461-1473.
10. Surry, D. S.; Buchwald, S. L., Biaryl Phosphane Ligands in Palladium-Catalyzed
Amination. Angew. Chem. Int. Ed. 2008, 47 (34), 6338-6361.
11. Zuccarello, G.; Zanini, M.; Echavarren, A. M., Buchwald-Type Ligands on Gold(I) Catalysis. Isr. J. Chem. 2020, 60 (3-4), 360-372.
12. Gessner, V. H., Modern Ylide Chemistry: Applications in Ligand Design, Organic and Catalytic Transformations. Springer: 2018; Vol. 177.
13. Kolodiazhnyi, O. I., Phosphorus ylides: chemistry and applications in organic synthesis. John Wiley & Sons: 2008.
14. Jörges, M.; Krischer, F.; Gessner, V. H., Transition Metal–Free Ketene Formation from Carbon Monoxide through Isolable Ketenyl Anions. Science 2022, 378 (6626), 1331-1336.
15. Lapointe, S.; Sarbajna, A.; Gessner, V. H., Ylide-Substituted Phosphines: A Platform of Strong Donor Ligands for Gold Catalysis and Palladium-Catalyzed Coupling Reactions. Acc. Chem. Res. 2022, 55 (5), 770-782.
16. Darmandeh, H.; Löffler, J.; Tzouras, N. V.; Dereli, B.; Scherpf, T.; Feichtner, K.-S.; Vanden Broeck, S.; Van Hecke, K.; Saab, M.; Cazin, C. S. J.; Cavallo, L.; Nolan, S. P.; Gessner, V. H., Au⋅⋅⋅H−C Hydrogen Bonds as Design Principle in Gold(I) Catalysis. Angew. Chem. Int. Ed. 2021, 60 (38), 21014-21024.
17. Dumas, J. B. Ann. Chim. Phys. 1835, 58, 28.
18. Arbuzov, B. A., 150th Anniversary of the Birth of A. M. Butlerov. Bulletin of the
Academy of Sciences of the USSR, Division of Chemical Science 1978, 27 (9), 1791-1794.
19. Hopkinson, M. N.; Richter, C.; Schedler, M.; Glorius, F., An Overview of N-
Heterocyclic Carbenes. Nature 2014, 510 (7506), 485-496.
20. Wanzlick, H. W.; Schönherr, H. J., Direct Synthesis of a Mercury Salt-Carbene
Complex. Angew. Chem. Int. Ed. Eng. 1968, 7 (2), 141-142. 106
21. Arduengo, A. J., III; Harlow, R. L.; Kline, M., A Stable Crystalline Carbene. J. Am. Chem. Soc. 1991, 113 (1), 361-363.
22. Lee, M.-T.; Hu, C.-H., Density Functional Study of N-Heterocyclic and Diamino Carbene Complexes: Comparison with Phosphines. Organometallics 2004, 23 (5), 976-983.
23. Doddi, A.; Peters, M.; Tamm, M., N-Heterocyclic Carbene Adducts of Main Group Elements and Their Use as Ligands in Transition Metal Chemistry. Chem. Rev. 2019, 119 (12), 6994-7112.
24. Powers, K.; Hering-Junghans, C.; McDonald, R.; Ferguson, M. J.; Rivard, E., Improved Synthesis of N-Heterocyclic Olefins and Evaluation of Their Donor Strengths. Polyhedron 2016, 108, 8-14.
25. Al-Rafia, S. I.; Malcolm, A. C.; Liew, S. K.; Ferguson, M. J.; McDonald, R.; Rivard, E., Intercepting Low Oxidation State Main Group Hydrides with a Nucleophilic N- Heterocyclic Olefin. Chem. Commun. 2011, 47 (24), 6987-6989.
26. Kuhn, N.; Bohnen, H.; Kreutzberg, J.; Bläser, D.; Boese, R., 1,3,4,5-Tetramethyl-2- Methyleneimidazoline—An Ylidic Olefin. J. Chem. Soc., Chem. Commun. 1993, (14), 1136-1137.
27. Naumann, S., Synthesis, Properties & Applications of N-Heterocyclic Olefins in Catalysis. Chem. Commun. 2019, 55 (78), 11658-11670.
28. Dumrath, A.; Wu, X.-F.; Neumann, H.; Spannenberg, A.; Jackstell, R.; Beller, M., Recyclable Catalysts for Palladium-Catalyzed C–O Coupling Reactions, Buchwald– Hartwig Aminations, and Sonogashira Reactions. Angew. Chem. Int. Ed. 2010, 49 (47), 8988-8992.
29. Paisley, N. R.; Lui, M. W.; McDonald, R.; Ferguson, M. J.; Rivard, E., Structurally Versatile Phosphine and Amine Donors Constructed from N-Heterocyclic Olefin Units. Dalton Trans. 2016, 45 (24), 9860-9870.
30. Wang, T.-H.; Chen, W.-C.; Ong, T.-G., Carbodicarbenes or Bent Allenes. J. Chin. Chem. Soc. 2017, 64 (2), 124-132.
31. Tonner, R.; Frenking, G., C(NHC)2: Divalent Carbon(0) Compounds with N- Heterocyclic Carbene Ligands—Theoretical Evidence for a Class of Molecules with Promising Chemical Properties. Angew. Chem. Int. Ed. 2007, 46 (45), 8695-8698.
32. Dyker, C. A.; Lavallo, V.; Donnadieu, B.; Bertrand, G., Synthesis of an Extremely Bent Acyclic Allene (A “Carbodicarbene”): A Strong Donor Ligand. Angew. Chem. Int. Ed. 2008, 47 (17), 3206-3209.
33. Chen, W.-C.; Hsu, Y.-C.; Lee, C.-Y.; Yap, G. P. A.; Ong, T.-G., Synthetic Modification of Acyclic Bent Allenes (Carbodicarbenes) and Further Studies on Their Structural Implications and Reactivities. Organometallics 2013, 32 (8), 2435-2442.
34. Kuhn, N.; Bohnen, H.; Kratz, T.; Henkel, G., Derivate des Imidazols, VII. 2,3- Dihydro-1,3,4,5-tetramethyl-2-methylen-1H-imidazol als Kupplungsreagens. Die Kristallstruktur von Bis(1,3,4,5-tetramethyl-2-imidazolyl)methylium-iodid. Liebigs Ann. Chem. 1993, 1993 (10), 1149-1151.
35. Chen, W.-C.; Shen, J.-S.; Jurca, T.; Peng, C.-J.; Lin, Y.-H.; Wang, Y.-P.; Shih, W.-C.; Yap, G. P. A.; Ong, T.-G., Expanding the Ligand Framework Diversity of Carbodicarbenes and Direct Detection of Boron Activation in the Methylation of Amines with CO2. Angew. Chem. Int. Ed. 2015, 54 (50), 15207-15212.
36. Liu, S.-k.; Chen, W.-C.; Yap, G. P. A.; Ong, T.-G., Synthesis of Carbophosphinocarbene and Their Donating Ability: Expansion of the Carbone Class. Organometallics 2020, 39 (23), 4395-4401.
37. Noshi, M. N.; El-Awa, A.; Fuchs, P. L., Second-Generation Synthesis of Syn-and Anti-Cycloheptadienylsulfone Polyketide Stereodiads. J. Org. Chem. 2008, 73 (8), 3274-3277.
38. Chen, W.-C.; Shih, W.-C.; Jurca, T.; Zhao, L.; Andrada, D. M.; Peng, C.-J.; Chang, C.-C.; Liu, S.-k.; Wang, Y.-P.; Wen, Y.-S.; Yap, G. P. A.; Hsu, C.-P.; Frenking, G.; Ong, T.-G., Carbodicarbenes: Unexpected π-Accepting Ability during Reactivity with Small Molecules. J. Am. Chem. Soc. 2017, 139 (36), 12830-12836.
39. Steyl, G., Trans-Dichlorobis (triphenylphosphine) Palladium (II) Dichloroethane Solvate. Acta Crystallogr. Sect. Sect. E: Struct. Rep. Online 2006, 62 (6), m1324- m1325.
40. Grushin, V. V.; Bensimon, C.; Alper, H., Dichlorobis(tricyclohexylphosphine)- palladium(II): Synthesis and Crystal Structure. An Exceptionally Simple and Efficient Preparation of Bis(tricyclohexylphosphine)palladium(0). Inorg. Chem. 1994, 33 (21), 4804-4806.
41. Scherpf, T.; Schwarz, C.; Scharf, L. T.; Zur, J.-A.; Helbig, A.; Gessner, V. H., Ylide- Functionalized Phosphines: Strong Donor Ligands for Homogeneous Catalysis. Angew. Chem. Int. Ed. 2018, 57 (39), 12859-12864.
42. Schmidbaur, H., Proof of Concept for Hydrogen Bonding to Gold, Au⋅⋅⋅H−X. Angew. Chem. Int. Ed. 2019, 58 (18), 5806-5809.
43. Muir, J. A.; Muir, M. M.; Pulgar, L. B.; Jones, P. G.; Sheldrick, G. M., Structures of Two Gold (I) Complexes with Tricyclohexylphosphine: [(Cy3P)AuCl] and
[(Cy3P)2Au]+Cl−. Acta Crystallogr. Sect. C: Cryst. Struct. Commun. 1985, 41 (8),
1174-1176.
44. Borissova, A. O.; Korlyukov, A. A.; Antipin, M. Y.; Lyssenko, K. A., Estimation of
Dissociation Energy in Donor−Acceptor Complex AuCl·PPh3 via Topological Analysis of the Experimental Electron Density Distribution Function. J. Phys. Chem. A 2008, 112 (46), 11519-11522.
45. Collado, A.; Nelson, D. J.; Nolan, S. P., Optimizing Catalyst and Reaction Conditions in Gold(I) Catalysis–Ligand Development. Chem. Rev. 2021, 121 (14), 8559-8612.
46.Huang, B.; Hu, M.; Toste, F. D., Homogeneous Gold Redox Chemistry: Organometallics, Catalysis, and Beyond. Trends in Chemistry 2020, 2 (8), 707-720.
47.Handelmann, J.; Babu, C. N.; Steinert, H.; Schwarz, C.; Scherpf, T.; Kroll, A.; Gessner, V. H., Towards the Rational Design of Ylide-Substituted Phosphines for Gold(I)- Catalysis: From Inactive to ppm-level Catalysis. Chem. Sci. 2021, 12 (12), 4329-4337.
48.Hashmi, A. S. K., Homogeneous Gold Catalysis Beyond Assumptions and Proposals—Characterized Intermediates. Angew. Chem. Int. Ed. 2010, 49 (31), 5232- 5241.
49. Wang, W.; Hammond, G. B.; Xu, B., Ligand Effects and Ligand Design in Homogeneous Gold(I) Catalysis. J. Am. Chem. Soc. 2012, 134 (12), 5697-5705.
50. Ma, Y.; Ali, H. S.; Hussein, A. A., A Mechanistic Study on the Gold(I)-Catalyzed Cyclization of Propargylic Amide: Revealing the Impact of Expanded-Ring N- Heterocyclic Carbenes. Catal. Sci. Technol. 2022, 12 (2), 674-685.
指導教授 陳銘洲 王朝諺 審核日期 2023-7-27
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