以過渡金屬催化合成具官能基碳環及異員環新途徑之發展

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研究生：	沙米爾 Samir Kundlik Pawar
論文名稱：	以過渡金屬催化合成具官能基碳環及異員環新途徑之發展 Development of New Synthetic Approaches to Access Functionalized Carbocycles and Heterocycles by Transition Metal Catalysis
指導教授：	劉瑞雄 Liu, Rai Shung
口試委員:	蔡易州 Tsai, Yi Chou 吳明忠 Wu, Ming Jung 侯敦仁 Hou, Duen Ren 陳銘洲 Chen, Ming Chou
學位類別：	博士 Doctor
系所名稱：	理學院 - 化學系 Department of Chemistry
論文出版年：	2015
畢業學年度：	103
語文別：	英文
論文頁數：	539
中文關鍵詞：	金催化、和環、炔醯胺、氧化加成、異員環
外文關鍵詞：	Gold-Catalyzed, Formal cycloaddition, Ynamides, oxidative cyclizations, Heterocycles
相關次數：	點閱：3 下載：0
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Abstract (Chinese)

本文描述使用金與銀鹽類之有機合成轉換的新途徑之發展。藉由軟性親炔的金屬可使易取得的基質經由溫和、非對映選擇性、高效率地轉換成多種碳環、含氮或氧之雜環。為了更清楚地瞭解本文，本文分成四個章節。
第一章主要探討2-乙炔基芐醚與有機氧化物透過金催化環加成反應合成1,3-二氫異衍生物。這類以1,3-二氫異苯基呋喃為核心的化合物是自然界中最常見的結構之一，且十分廣泛的被應用在重要的結構以及生物學中。這種產物的核心結構是通過[4+ 1]環-α-羰卡賓和系留式醚類所構成。該催化劑的效用包括對苯基和不同醚類的各種取代。
第二章論述金以及銀催化炔醯胺、芳基氧雜環丁烷和芳基氮雜環丁烷進行一[4+2]環加成反應，形成六元雜環。氧雜環丁烷做為親核劑，而金--炔醯胺則為親電劑。在氮雜環丁烷的案例中，我們發現銀六氟銻比金催化劑更有效催化炔醯胺之[4+2]-環加成。此二環加成反應適用在合理的範圍內之炔醯胺、氧雜環丁烷以及氮雜環丁烷，進而表現其合成六元雜環之實用性，如6-氨基-3,4-二氫-2氫-吡喃和2-氨基-1,4,5,6-四氫吡啶。
第三章介紹炔醯胺分別與2H-氮環丙烯、疊氮烯烴透過金催化進行環加成，得到兩個不同類別的[3+2]或[4+3]環加成物。炔醯胺與2H-氮環丙烯類的環加成反應可得到吡咯類產物。而對於苯基取代富含電子的炔醯胺，與疊氮烯烴通過新穎的[4+ 3]環加成反應來形成-1H-苯基-[d]-氮雜產物。
第四章介紹透過共激活模式以1,6-二炔與-8-甲基喹啉N-氧化物合成出3-酮萘酚和3-酮基酚衍生物合成方法之發展。本反應的價值反應在其適用於廣泛的苯和非苯類衍生基質。

Abstract
This dissertation describes development of new synthetic organic transformations by using gold and silver salts. The use of these soft alkynophilic metals enables mild, diastereoselective and efficient transformations of a variety of readily available substrates to wide range of synthetically useful carbocyclic and nitrogen or oxygen containing heterocyclic products. For better understanding the thesis is divided into four chapters.
The first chapter deals with the Gold-catalyzed reactions of 2-ethynylbenzyl ethers with organic oxides for synthesis of 1,3-dihydroisobenzofuran derivatives through a formal cycloaddition reaction. Such 1,3-dihydroisobenzofuran core is one of the most commonly encountering skeletons in nature and the core scaffold has a wide spread application in structural and biological importance. The core structures of the resulting products are constructed through a formal [4+1] cycloaddition among α-carbonyl carbenoids and tethered ethers. The utility of this catalysis includes various substituents on phenyl groups and different ethers.

The second chapter deals with the Gold- and Silver-catalyzed [4+2] cycloaddition reactions of ynamides with aryl-oxetanes and aryl-azetidines to form six membered heterocycles. Oxetanes function as nucleophiles whereas gold--ynamides are present as electrophiles. In the case of azetidines, silver hexafluoroantimonate was found to be more active than gold catalyst in their [4+2]-cycloadditions with ynamides. The two cycloadditions are applicable to a reasonable range of ynamides, oxetanes and azetidines, thus manifesting their synthetic utility to access six-membered heterocycles such as 6-amino-3,4-dihydro-2H-pyrans and 2-amino-1,4,5,6-tetrahydropyridines.

The third chapter describes the Gold-catalyzed cycloadditions of ynamides with azidoalkenes or 2H-azirines to give [3+2] or [4+3] formal cycloadducts of two different classes. Cycloadditions of ynamides with 2H-azirine species afford pyrrole products. For ynamides substituted with an electron-rich phenyl group, their reactions with azidoalkenes proceed through novel [4+3] cycloadditions to deliver 1H-benzo[d]azepine products instead.

The fourth chapter presents development of a oxidative cyclizations of 1,6 diynes with 8-methylquinoline N-oxides through dual activation mode to achieve 3-keto naphthols and 3-keto phenol derivatives. The value of the reaction is reflected by their applicability to a broad range of benzene- and nonbenzene-derived substrates.

Contents

Acknowledgement                                                            IV   
Abstract                                                        VI
List of Schemes                                                   IX
List of Table                                               XIII
List of Figures                                                                                                     XIV
List of Publications                                              XV 
Abbreviations                                                 XVI










Chapter I: Gold-Catalyzed Formal Cycloadditions of 2-Ethynylbenzyl Ethers with Organic    Oxides.    
    Introduction                                                  2
Results and Discussion                                        10
Conclusion                                                17
Experimental Procedure                                        18
Spectroscopic Data                                            23
Reference                                                35
HPLC Data                                                40
1H and 13C NMR Spectra                                              43

Chapter II: Gold- and Silver-catalyzed [4+2] Cycloadditions of Ynamides with Oxetanes and Azetidines.    
    Introduction                                              118
Results and Discussion                                      126
Conclusion                                              137
Experimental Procedure                                      137
Spectroscopic Data                                          141
Reference                                              160
X-ray Crystallographic Data                                      165
1H and 13C NMR Spectra                                            184

Chapter III: Diversity in Gold-catalyzed Formal Cycloadditions of Ynamides with Azidoalkenes or 2H-Azirines: [3+2]- Versus [4+3]-Cycloadditions.
Introduction                                              273
Results and Discussion                                      281
Conclusion                                              292
Experimental Procedure                                      292
Spectroscopic Data                                          296
Reference                                              313
X-ray Crystallographic Data                                      316
1H and 13C NMR Spectra                                            336

Chapter IV: Gold Catalyzed Oxidative Cyclizations of 1,6 Diynes : Synthesis of 3-keto naphthols or 3-keto phenol derivatives.
Introduction                                              432
Results and Discussion                                      439
Conclusion                                              446
Experimental Procedure                                      446
Spectroscopic Data                                          450
Reference                                              462
X-ray Crystallographic Data                                      464
1H and 13C NMR Spectra                                            470
List of Schemes
Chapter I
Scheme 1: Intramolecular and intermolecular approach to access -oxo gold                        4
 carbenes from alkynes 
Scheme 2:  Rearrangement alkynyl sulfoxides catalyzed by gold(I) complexes                            5
Scheme 3: Synthesis of tetrahydrobenz[b]azepin-4-ones via intramolecular                   5
-oxo gold carbenoid generation                                         
Scheme 4:  First example of accessing -oxo gold carbenes via intermolecular                   6
       oxidation of terminal alkynes                      
Scheme 5: Gold catalyzed synthesis of oxetan-3-ones from propargylic alcohols                  6
Scheme 6: Gold-catalyzed [2+2+1] annulation of alkynes to synthesize 2,5                                 7
                  disubstituted oxazoles.
Scheme 7: Oxidative cyclization of 1,5 enyne via 5-exo dig mode                                                7
Scheme 8: Oxidative cyclization of 1,5 enyne via 5-endo dig mode                                              8
Scheme 9: Gold(I)-catalyzed intramolecular cycloaddition of alkynes                                          8
Scheme 10: Gold catalyzed intermolecular (4+2) cycloaddition of                           9
       o-alkynylbenzaldehydes with external alkynes                 
Scheme 11: Gold(I)-catalyzed formal cycloaddition of ethynylbenzyl ethers 1-1 with               9 8-methylquinoline N-oxide                                                                                  
Scheme 12: Gold(I)-catalyzed carboalkoxylation of ethynylbenzyl ethers 1                                   10
Scheme 13: Preparation of 1-(dimethoxymethyl)-2-ethynylbenzene (1-1a)                                   12
Scheme 14: Trapping of α-oxo carbene intermediacy                                                           15
Scheme 15: Chirality transfer experiment                                                            16
Scheme 16: A proposed mechanism for formal cycloadditions                                                    17  
Chapter II
Scheme 1: Palladium catalyzed cycloadditions of azetidines with carbodiimides                 119
Scheme 2: BF3.Et2O catalyzed [4+2] cycloadditions of azitidines with electron               120
rich alkenes          
Scheme 3: BF3.Et2O catalyzed [4+2] cycloaddition reactions of azetidines                   120
 with nitriles
Scheme 4: Zn(OTf)2 catalyzed [4+2] cycloaddition reactions of azetidines with nitriles          121
Scheme 5: Cu(OTf)2 mediated [4+2] cycloaddition reactions of azetidines with               121
 various aldehydes 
Scheme 6: Asymmetric ring expansion of oxetanes according to Katsuki and               122
co-workers 
Scheme 7: Ring expansion of asymmetric oxetanes according to Lo and Fu.                          122
Scheme 8: [3+2]-Cycloadditions of alkynes with aziridines                                      123
Scheme 9: FeCl3-catalyzed [3+2] cycloadditions of aziridines with arylalkynes              123
Scheme 10: Interactions of ynamides with gold catalysts                                       124
Scheme 11: Gold-catalyzed  [4+2]  cycloadditions of ynamides  with alkenes                              124
Scheme 12: Gold catalyzed [4+3]-cycloadditions of ynamides with epoxides                      125
Scheme 13: Gold catalyzed [4+2]-cycloadditions of ynamides with four                           126
        membered ring heterocycles
Scheme 14: General synthetic procedure for synthesis of ynamide (2-1a)                                  128
Scheme 15: Functinalizations of heterocycles 2-3a and 2-5a                                        135    
Scheme 16: Plausible mechanisms for [4+2] cycloadditions                          135
Chapter III
Scheme 1: Activities of organic azides as 1,3 dipoles and nitrene equivalents              274
Scheme 2: Thermolysis of vinyl azides into 2H-azirines                          274
Scheme 3: Synthesis of polysubstituted pyrroles by simple heating of vinyl azides           275
      and 1,3-dicarbonyl compounds
Scheme 4: Manganese(III)-catalyzed formal [3+2]-annulation of vinyl azides with                 276
      1,3-dicarbonyl compounds 
Scheme 5: Synthesis of highly substituted isoquinolines from -aryl vinyl azides and           276
      internal alkynes
Scheme 6: Metal free visible-light-induced formal [3+2] cycloaddition for synthesis           277
      of pyrroles 
Scheme 7: Behavior of ynamides with gold catalysts                          278
Scheme 8: Gold-catalyzed  [4+2] and [2+2+2]  cycloadditions of ynamides with               278
      alkenes 
Scheme 9: Gold catalyzed [4+2]-cycloadditions of ynamides with oxetanes and               279
      azetidines 
Scheme 10: Gold catalyzed [3+2]-cycloadditions of ynamides with 2H-azirines               280
Scheme 11: Gold catalyzed  [3+2] Vs [4+3]-cycloadditions of ynamides with vinyl          281
        azides 
Scheme 12: General synthetic procedure for synthesis of ynamide (3-1a)                  283
Scheme 13: General synthetic procedure for synthesis of vinyl azide (3-2a)              284
Scheme 14: The formal [3+2] and [4+3] cycloadditions of ynamides 3-1a and 3-5g           289
         with 2H-azirine
Scheme 15: Proposed reaction mechanisms for diverse products                      290
Scheme 16: Exclusion of possibility of gold carbene intermediacy                      291
Chapter IV
Scheme 1: Intramolecular and intermolecular approach to access -oxo gold               433
      carbenes from alkynes
Scheme 2: Rearrangement alkynyl sulfoxides catalyzed by gold(I) complexes               434
Scheme 3: Synthesis of tetrahydrobenz[b]azepin-4-ones via intramolecular -oxo gold          434
                  carbenoid generation
Scheme 4: First example of accessing -oxo gold carbenes via intermolecular oxidation           435
      of terminal alkynes 
Scheme 5: Gold catalyzed synthesis of oxetan-3-ones from propargylic alcohols              435
Scheme 6: Gold catalyzed oxidative cyclization of ethynylbenzyl ethers with               436
       8-methylquinoline N-oxide 
Scheme 7: Gold-Catalyzed Oxidative Diyne Cyclizations                            436
Scheme 8: Gold-catalyzed cycloisomerization of 1,6-diyne carbonates and esters to           437    
      2,4a-dihydro‑1H‑fluorenes  
Scheme 9: Gold-catalyzed oxidation of internal alkynes to access enone derivatives           438                                                                                      
Scheme 10: Gold(I)-catalyzed oxidative cyclizations of 1,6 diynes 4-1 with               438
        8-methylquinoline N-oxide 
Scheme 11: General synthetic procedure for synthesis of 1,6 diynes (4-1a)               441
Scheme 12: General synthetic procedure for synthesis of 1,6 diynes (4-1j and 4-1k)          441
Scheme 13: Plausible mechanism for oxidative cyclization of 1,6 diyne                          445
List of Tables
Chapter I
Table 1: Gold-catalyzed cycloaddition of 2-ethynylphenylacetal (1-1a) over                 11
   various catalysts
Table 2: Reaction scope for various acetal substrates 1-1                            13
Chapter II
Table 1: Condition optimization for cycloaddition of ynamides with oxetanes                      126
Table 2: Reaction scope of cycloadditions between ynamide 2-1 and oxetanes 2-2              129
Table 3: Condition optimization for cycloaddition of ynamides with azetidines                132
Table 4: Reaction scope of cycloadditions between ynamide 2-1 and azetidines 2-4            133
Chapter III
Table 1: Condition optimization for formal cycloadditions of ynamides with               282
               vinyl azides 
Table 2: Scope of the gold-catalyzed [3+2] cycloadditions of various ynamides with           285
   vinyl azides 
Table 3: Scope of the gold-catalyzed [4+3] cycloadditions of various ynamides with           287
   vinyl azides
Chapter IV
Table 1: Condition optimization for oxidative cyclizations of 1,6 diynes                  439
Table 2: The scope of gold-catalyzed oxidative cyclizations of 1,6 diynes                   442

List of Figures
Chapter I
Figure 1: Singlet and triplet carbenes                                                                                      2
Figure 2: Fischer and schrock carbenes                                                                                 3
Figure 3: List of Substrates                                                                                           12
Figure 4: Bioactive compounds bearing dihydroisobenzofuran structure                    18
Chapter II
Figure 1: List of substrates                                                                                   127
Figure 2:  ORTEP diagram of compound 2-3k, 2-5b and 2-6a                              136
Chapter III
Figure 1: List of substrates                                                                                  283
Figure 2:  ORTEP diagrams of 2-3c and 2-6a                                                                      291
Chapter IV
Figure 1: List of substrates                                                                                   440
Figure 1: ORTEP diagram of compound 4-2h                                445

                                

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28. For metal-catalyzed carboalkoxylations of alkynes; see selected examples: a) Dubé, P.; Toste, F. D. J. Am. Chem. Soc. 2006, 128, 12062. b) Fürstner, A.; Szillat, H.; Stelzer, F. J. Am. Chem. Soc. 2000, 122, 6785. c) Fürstner, A.; Stelzer, F.; Szillat, H. J. Am. Chem. Soc. 2001, 123, 11863. d) Shimada, T.; Nakamura, I.; Yamamoto, Y. J. Am. Chem. Soc. 2004, 126, 10546. f) Nakamura, I.; Mizushima, Y.; Yamamoto, Y. J. Am. Chem. Soc. 2005, 127, 15022.
29. Braga, A. L.; Ludrke, D. S.; Vargas, F.; Paixáo, M. W. Chem. Commun. 2005, 2512.
30. Species (R)-(+)-1-2k (93.9 % ee) was treated with ozone to give (R)-(- )-1-5a ([] = -39.6, CHCl3). This R-enantiomer was reported to have [] = -48.6 in CHCl3; see Ramachandran, P. V.; Chen, G.-M.; Brown, H. C. Tetrahedron Lett. 1996, 37, 2205.

31. Selected examples: a) Lu, B.; Li, C.; Zhang, L. J. Am. Chem. Soc. 2011, 132, 14070. b) Dateer, R.-B.; Shaibu, B. S.; Liu, R.-S. Angew. Chem. 2012, 124, 117; Angew. Chem. Int. Ed. 2012, 51, 113.
32. Karad, S. N.; Bhunia, S.; Liu, R.-S. Angew. Chem. 2012, 124, 8852; Angew. Chem. Int. Ed. 2012, 51, 8722.
33. We exclude a double inversion mechanism for the retention of stereochemistry; this process presumably involves the attack of OTf- on intermediate D in Scheme 22. However, the use of LAuSbF6 on R-(+)-1-k (90.5 %) gave desired R-(-)-1-2k with 90.5 % ee, thus excluding its possibility.
34. a) Harper, J. K.; Arif, A. M.; Ford, E. J.; Strobel, G. A.; Porco, J. A. Jr.; Tomer, D. P.; Oneill, K. L.; Heider E. M.; Grant, D. M. Tetrahedron. 2003, 59, 2471. b) Moore, N.; Verdoux, H.; Fantino, B. Int. Clin. Psychopharmacol. 2005, 20, 131. c) Andrews, S. W.; Guo, X.; Zhu, Z.; Hull, C. E.; Wurster, J. A.; Wang, S.; Wang, E. H.; Malone, T. US Pat. USXXCO US 20060004084 A1 20060105, CAN 144: 108205, An 2006: 14038., 2006, p. 316. d) Lin, G.; Chan, S. S.-K.; Chung, H.-S.; Li, S.-L. in Studies in Natural Products Chemistry, Vol. 32 (Ed.: Atta-ur-Rahman), Elsevier, Amsterdam, 2005, pp. 611. e) Karmakar, R.; Pahari, P.; Mal, D. Chem. Rev. 2014, 114, 6213.

Chapter 2
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3. a) Undheim, K. T. Benneche, in Comprehensive Heterocyclic Chemistry II, Vol. 6 (Eds.: Katritzky, A. R.; Rees, C. W.; Scriven, E. F. V.; McKillop A.), Pergamon, Oxford, 1996, p. 93. b) Michael, J. P. Nat. Prod. Rep. 2005, 22, 627. c) Joule, J. A.; Mills, K. in Heterocyclic Chemistry, 4th ed., Blackwell, Cambridge, 2000, p. 194. d) Erian, A.W. Chem. Rev. 1993, 93, 1991.
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33. a) Davies, P.W.; Cremonesi, A.; Dumitrescu, L. Angew. Chem. 2011, 123, 9093; Angew. Chem. Int. Ed. 2011, 50, 8931. b) Hashmi, A. S. K.; Buhrle, M.; Wolfle, M.; Rudolph, M. Wieteck, M.; Rominger, F.; Frey, W. Chem Eur. J. 2010, 16, 9846. c) Evano, G.; Coste, A.; Jouvin, K. Angew. Chem. 2010, 122, 2902; Angew. Chem. Int. Ed. 2010, 49, 2840.
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35. X-ray crystallographic data of compounds 2-3k, 2-5b, and 2-6a was deposited in Cambridge Crystallographic Data Center (CCDC for 2-3k-979491, 2-5b-979492, and 2-6a -979495).

chapter 3
1. See reviews: a) Boger, D. L. Chem. Rev. 1986, 86, 781. b) Pindur, U.; Lutz, G.; Otto, C. Chem. Rev. 1993, 93, 741. c) Nicolaou, K. C.; Snyder, S. A.; Montagnon, T.; Vassilikogiannakis, G. Angew. Chem. Int. Ed. 2002, 41, 1668. d) Trost, B. M. Acc. Chem. Res. 2002, 35, 695. e) Trost, B. M. Angew. Chem. 1995, 107, 285; Angew.Chem. Int. Ed. 1995, 34, 259. f) Trost, B. M. Science. 1991, 254, 1471. g) Benbow, J. F.; McClure, K. F.; Danishefsky, S. J. J. Am. Chem. Soc. 1993, 115, 12305. h) McClure, K.; Benbow, J. F.; Danishefsky, S. J. J. Am. Chem. Soc. 1991, 113, 8185.
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13. Xuan, J.; Xia, X.-D.; Zeng, T.-T.; Feng, Z.-J.; Chen, J.-R.; Lu, L.-Q.; Xiao, W.-J. Angew. Chem. Int. Ed. 2014, 53, 5653.
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17. For metal-catalyzed cycloaddition reactions, see selected reviews: a) Wender, P. A.; Verma, V. A.; Paxton, T. H. Acc. Chem. Res. 2008, 41, 40. b) Lautens, M.; Klute, W.; Tam, W. Chem. Rev. 1996, 96, 49. c) Inglesby, P. A.; Evans, P. A. Chem. Soc. Rev. 2010, 39, 2791. d) Hashmi, A. S. K. Chem. Rev. 2007, 107, 3180. e) López, F.; Mascareñas, J. L. Beilstein J. Org. Chem. 2011, 7, 1075. f) C. Aissa In Comprehensive Organic Synthesis II, Elsevier, P. Knochel; G. A. Molander Eds., 5.35, pp 1738. g) Mascareńas, J. L.; Lopez, G. F. In Comprehensive Organic Synthesis II, Elsevier, P. Knochel; G. A. Molander Eds., 5.13, pp 595.
18. a) The Chemistry of the Azido Group (Ed.: S. Patai), Wiley, New York USA, 1971. b) The Chemistry of Halides, Pseudo-halides and Azides, Supplement D, (Eds.: S. Patai, Z. Rappoport), Wiley, Chichester UK 1983. c) Chemistry of Halides, Pseudo-Halides and Azides, Part 1 (Ed.: S. Patai), Wiley, Chichester UK, 1995. d) Azides and Nitrenes -Reactivity and Utility (Ed.: E. F. V. Scriven), Academic Press, New York USA, 1984.
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21. For gold-catalyzed intramolecular cyclizations of 2H-azirine with a tethered alkyne, see Prechter, A.; Henrion, G.; Bel, P. F.; Gagosz, F. Angew. Chem. Int. Ed. 2014, 53, 4959; Angew. Chem. 2014, 126, 5059.
22. a) Nitta, M.; Kobayashi, T. Chem. Lett. 1983, 1715. b) Nitta, M.; Kobayashi, T. Bull. Chem. Soc. Jpn. 1984, 57, 1035.
23. For gold catalyzed [4+3]-cycloadditions, see recent examples: a) Karad, S. N.; Bhunia, S. Liu, R.-S. Angew. Chem. Int. Ed. 2012, 51, 8722; Angew. Chem. 2012, 124, 8852. b) Gulas, M.; Lopez, F.; Mascarenas, J. L. Pure Appl. Chem. 2011, 83, 495. c) Maulen, P.; Zeldin, R. M.; Gonzalez, A. Z.; Toste, F. D. J. Am. Chem. Soc. 2009, 131, 6348. d) Alonso, I. ; Faustino, H.; Lopez, F.; Mascarenas, J. L. Angew. Chem. Int. Ed. 2011, 50, 11496; Angew. Chem. 2011, 123, 11698. e) Alonso, I.; Trillo, B.; Lopez, F.; Montserrat, S.; Ujaque, G.; Castedo, L.; Lledos, A.; Mascarenas, J. L. J. Am. Chem. Soc. 2009, 131, 13020. f) Wang, T.; Zhang, J. Chem. Eur. J. 2011, 17, 86. g) Zhang,Y.; Liu, F.; Zhang, L. Chem. Eur. J. 2010, 16, 6146.
24. X-ray crystallographic data of compounds 3-3c and 3-6a are deposited at Cambridge Crystallographic Data Center: 3-3c (CCDC 1042641) and 3-6a (CCDC 1042642).

chapter 4
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18. X-ray crystallographic data of compound 4-2h was deposited in Cambridge Crystallographic Data Center (CCDC for 4-2h:1409464).

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