摘要
本論文描述了使用金和銅的催化劑來開發新合成方法來進行有機物轉化，使用這些金屬可以進行溫和、選擇性及有效的轉化，從而可以從容易取得的底物中得到一系列碳氧化、碳環、苯並環狀和雜環的產物，為了便於理解，此論文分為四個章節詳細介紹。

第一章節中利用3-烯-1-炔胺與烯丙基和炔丙醇通過非克萊森途徑進行的金催化1,4-羧基氧化反應組成，金催化的克萊森途徑與炔烴的反應在文獻中是眾所皆知的。但金催化3-烯-1-酰胺與烯丙醇和炔丙醇的1,4-碳氧化反應通過非克萊森途徑產生-不飽和酰胺，該機制涉及初始金烯醇醚的電離以形成C-結合的金二烯醇鹽，其捕獲烯丙基或炔丙基陽離子以產生觀察到的產物。我們利用18O-標記實驗排除了對這些3-烯-1-酰胺的直接金催化烯丙基化或炔丙基化。

第二章節中由三種不同的炔酰胺和1-炔-3-醇催化環化策略組成，在此使用金催化劑在一鍋化操作方式可以有效地生產所得的碳環和雜環，這些環的化學選擇性受到酰胺類和1-炔-3-醇的取代基變化控制，該反應順序包括酰胺化合物的初始烷氧基化，然後是炔丙基烯醇醚的克萊森重排，並以1-烯丙基-5-酰胺中間體的6-endo-trig環化反應結束，在這一連串的環化反應中，5-烯丙基-1-酰胺環化產生5,6-二氫-2-吡喃酮和6-亞烷基環己-2-烯-1-甲酰胺在文獻中是前所未有的。

第三章節中由新的金催化[4+3]-3-烯-1-炔酰胺與異噁唑的混合物組成，可有效地提供4H-氮雜卓，該過程涉及金穩定的3-氮雜庚三烯基陽離子的6電子環化，在Zn(OTf)2存在下，所得的4H-氮雜卓經歷骨架重排以提供取代的吡啶衍生物，我們隨後在相同的3-烯-1-酰胺和異噁唑之間開發了新的催化[4+2]-環化，此環化反應我們是利用Au(I)/Zn(II)催化劑遞送取代的吡啶產物，在這項工作中報告了文獻報導中史無前例的六噻吩基陽離子電離環化的首次成功。

第四章節中由銅催化的[4+2]鄰炔基苯甲醛與異噁唑的苯並環化組成，可有效地得到萘酮衍生物，在此我們提出了苯並環化過程的合理反應機理顯示鄰炔基苯甲醛與Cu鹽的三鍵配位，隨後羰基氧對缺電子炔的親核攻擊，形成異喹啉(或異苯並噻吩)陽離子中間體，然後與異噁唑進行狄耳士–阿爾德反應，該過程涉及在3,4位上的異噁唑的環加成，這在文獻中是前所未有的，在3和5號位的3,5-二取代的異噁唑、異噁唑、單取代的異噁唑耐受程度都表現良好，而芳基取代的異噁唑不適用於該方法。

Abstract

This dissertation describes development of new synthetic organic transformation using gold and copper catalysts. The use of these metals enables mild, selective and efficient transformation to give a range of carbooxygenated, carbocyclic, Benz annulated and heterocyclic products from readily available substrates. This thesis is divided into four chapters for ease of understanding.
Chapter I is comprised of gold-catalyzed 1,4-Carbooxygenation reactions of 3-en-1-ynamides with allylic and propargylic alcohols via Non-Claisen Pathways. Gold catalyzed Claisen reactions with alkynes are well known in literature. But gold-catalyzed 1,4-carbooxygenations of 3-en-1-ynamides with allylic alcohols and propargylic alcohols yield -unsaturated amides through non-Claisen pathways; the mechanisms involve ionization of the initial gold enol ethers to form C-bound gold dienolates that capture allylic or propargylic cations to yield the observed products. Our 18O-labeling experiments exclude a direct gold-catalyzed allylation or propargylation on these 3-en-1-ynamides.




Chapter II is comprised of three distinct strategies for catalytic annulations between ynamides and 1-yn-3-ols; the resulting carbo- and heterocycles were produced efficiently in one-pot operations using a gold catalyst. The chemoselectivities of these annulations are controlled by variations of the substituents of the ynamides and the 1-yn-3-ols. This reaction sequence involves initial alkoxylations of ynamides, followed by Claisen rearrangement of propargylic enol ethers, and ends with 6-endo-trig cyclizations of 1-allenyl-5-amide intermediates. Among these cascade annulations, the cyclizations of 5-allenyl-1-amides to yield 5,6-dihydro-2-pyranones and 6-alkylenecyclohex-2-ene-1-carboxamides are unprecedented in the literature.





Chapter III is comprised of new gold-catalyzed [4+3]-annulations of 3-en-1-ynamides with isoxazoles which afford 4H-azepines efficiently; this process involves 6 electrocyclizations of gold-stabilized 3-azaheptatrienyl cations. In the presence of Zn(OTf)2, the resulting 4H-azepines undergo skeletal rearrangement to furnish substituted pyridine derivatives. We subsequently developed new catalytic [4+2]-annulations between the same 3-en-1-ynamides and isoxazoles to deliver substituted pyridine products using Au(I)/Zn(II) catalysts. This work reports the first success of the 6 electrocyclizations of heptatrienyl cations that are unprecedented in literature reports.





Chapter IV is comprised of copper-catalyzed [4+2] benzannulation of o-alkynyl benzaldehyde with isoxazole which affords napthyl ketone derivative efficiently. A plausible reaction mechanism for the present benzannulation process shows the coordination of the triple bond of o-alkynyl benzaldehyde with Cu-salt followed by subsequent nucleophilic attack of the carbonyl oxygen to the electron-deficient alkyne to form an isochromenylium (or Isobenzopyrilium) cationic intermediate which then undergoes Diels-Alder type reaction with isoxazole. This process involves a cycloaddition of isoxazole at 3,4 positions which is unprecedented in literature. 3,5-di-substituted isoxazole, isoxazole, mono-substitued isoxazole at 3 and 5 positions were well tolerated whereas aryl substituted isoxazoles were inapplicable to this method.

Table of Contents


List of Chapters
X
List of Schemes
XII
List of Tables
XIV
List of Figures
XIV
List of Publications
XVI
Abbreviations
XVII












List of Chapters
Chapter I: Gold-Catalyzed 1,4-Carbooxygenation of 3-En-1-ynamides with Allylic and Propargylic Alcohols via Non-Claisen Pathways
[Sovan Sundar Giri, Li-Hsuan Lin, Prakash Daulat Jadhav, and Rai-Shung Liu*, Adv. Synth. Catal. 2017, 359, 590 – 596.]

Introduction 2
Result and Discussion 14
Conclusion 28
Experimental Procedure 29
Spectral Data 35
Reference 56
X-ray Crystallographic Data 63
1H and 13C NMR Spectra 71
1H NOE 173

Chapter II: Gold-Catalyzed [4+2]- and [3+3]-Annulations of Ynamides with 1-Yn-3-ols to Access Six-Membered Carbocycles and Oxacycles via Three Distinct Cyclizations
[Sovan Sundar Giri and Rai-Shung Liu*, Adv. Synth. Catal. 2017, 359, 3311 – 3318.]

Introduction 182
Result and Discussion 191
Conclusion 207
Experimental Procedure 207
Spectral Data 212
Reference 235
X-ray Crystallographic Data 243
1H and 13C NMR Spectra 284
1H NOE 398

Chapter III: Gold-catalyzed [4+3]- and [4+2]-annulations of 3-en-1-ynamides with isoxazoles via novel 6-electrocyclizations of 3-azaheptatrienyl cations
[Sovan Sundar Giri and Rai-Shung Liu*, Chem. Sci., 2018, 9, 2991–2995.]

Introduction 406
Result and Discussion 417
Conclusion 431
Experimental Procedure 431
Spectral Data 437
Reference 460
X-ray Crystallographic Data 468
1H and 13C NMR Spectra 509
1H NOE 623

Chapter IV: Cu-catalyzed [4+2] cycloadditions of isoxazoles with enynals: An access to highly substituted naphthalene frameworks
[Sovan Sundar Giri and Rai-Shung Liu*, unpublished]

Introduction 632
Result and Discussion 638
Conclusion 647
Experimental Procedure 647
Spectral Data 652
Reference 662
X-ray Crystallographic Data 666
1H and 13C NMR Spectra 688

Chapter-I
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Chapter-II
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Chapter-III
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Chapter-IV
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