本文介紹了金及銀金屬催化之新合成方法製成高度官能之碳環和雜環有機分子。其中包括使用金和銀金屬將各種方便取得的基質高效轉化為廣泛、多功能的碳環和雜環產物。為了方便理解，本文被分為四個章節。
第一章描述了以金催化使硝基芳烴及丙炔酸衍生物進行1,2-胺基硝基化產生α-亞胺腈；這種新的反應適用於不同的丙炔衍生物和硝基芳烴來產生各種實用的1,2-氧化官能基化的炔類，而此結構設計可以應用於農業用藥之中。
第二章論述金金屬催化行亞胺化/曼尼希反應，經由連續反應使容易取得的3-烯-1-炔醯胺透過一鍋化高位向選擇性反應轉變為1,5-亞胺基化合物。該反應與多元化的3-烯-1-炔醯胺、醛和苯胺都可進行，且具有優良的非對映選擇性及產率。我們的對照實驗指出3-烯-1-炔醯胺之金催化胺化，得到α亞氨基烯丙基金中間體，隨後再與亞胺離子反應，進行立體選擇性的曼尼希反應。若以那些無環烯烴3-烯-1-炔醯胺進行反應則反應無選擇性，而若使用環烯烴類則具有順式選擇性。一個開放的過渡狀態使我們能夠合理的推測這些觀測到的立體選擇性是經由一個antiperiplanar構象所產生。

第三章描述了經由兩個不同的途徑利用金金屬催化炔醯胺、丙二烯酰胺以及α-芳香基重氮腈進行[3 + 2]環化得到1-胺基-1H-茚；這些環化的成功歸功於α氰基芳基卡賓用來激活離子通道的高親電性。茚分子是極為需要的天然產物，所得之1-氨基-1H-茚可以被用於生物活性分子的合成。
第四章介紹了新穎的金金屬催化吲哚及α-芳腈重氮進行分子間卡賓官能基化： 通過雙親核加成反應可以合成雙吲哚基-2-苯基乙腈。本反應顯示各種範圍的官能基容忍度及相對應的產率，這可以應用在許多吲哚生物鹼如砷啉A和砷啉B，抑制劑，吲哚-3-甲醇和Streptindole的核心結構上，這些是在許多治療疾病非常有用的分子。

This dissertation describes Gold & Silver-Catalyzed New Synthetic Methods to Access Highly Functionalized Carbocyclic and Heterocyclic Organic Molecules. It includes gold and silver metal which promotes efficient transformations of a variety of readily available substrates to wide range of synthetically useful carbocyclic and heterocyclic products. For better understanding, this thesis has been divided into four chapters
The first chapter describes the Gold-Catalysed 1,2-iminonitronation of propiolate derivatives with nitrosoarenes to give α-imidoyl nitrones; This new reactions are applicable to diverse propiolate derivatives and nitrosoarenes to implement 1,2-oxidative functionalization of alkynes which finds various application in Agrochemicals.
The second chapter deals with the Gold-Catalysed imination/Mannich reaction cascades on readily available 3-en-1-ynamides enable the diastereoselective synthesis of 1,5-iminoamino compounds in one-pot operation. The reactions work well with diversified 3-en-1-ynamides, aldehydes and anilines with good to excellent diastereoselectivities. Our control experiments indicate gold-catalyzed aminations of 3-en-1-ynamides to yield -imino allylgold intermediates that react subsequently with iminiums to implement the Mannich reactions stereoselectively. The reactions proceed with anti-selectvity for those 3-en-1-ynamides bearing acyclic alkenes whereas syn-selectivity is for their cycloalkene-based analogues. An open-transition state can satisfactorily rationalize these observed stereoselectivities based on an antiperiplanar conformation.
The third chapter describes Gold-catalyzed [3+2]-annulations of α-aryl diazonitriles with ynamides and allenamides yield 1-amino-1H-indenes in two distinct pathways; the success of these annulations relies on the high electrophilicity of α-cyano arylgold carbenes to activate an ionic pathway. Indene molecule is highly desirable moiety in natural product and the resulting 1-amino-1H-Indenes can be used for the synthesis of bioactive molecules.
The fourth chapter show development of novel Gold-Catalyzed intermolecular carbenoid functionalization of indoles with α-aryl diazo nitrile: Synthesis of bis(indolyl)-2-phenylacetonitrile via Double nucleophilic Addition Reaction. Reactions shows variety of scopes and yield a BIMs derivatives which is the core structures in many indole alkaloids such as Arsindoline A and B, Arundine, Viberindole A and Streptindole, these are very useful molecule in the treatment of many deseases.

List of Schemes
Chapter I

Scheme 1: Acess to α-oxo-gold-carbenes: Intra- vs intermolecular oxidation 4
Scheme 2: 1,2-Difuntionalization of Aminoalkynes using Oxidants 5
Scheme 3: AuBr3-catalyzed cyclization reaction of o-(alkynyl) nitrobenzene 5
Scheme 4: [3+2]-Annulations of nitrosoarenes and alkynes 6
Scheme 5: Oxidative [3+2]-cycloadditions for 1,5-enynes 7
Scheme 6: Reaction mechanisms for oxidative [4C+2]-cycloadditions 8
Scheme 7: regioselective umpolung reaction using alkynyl aldehydes 9
Scheme 8: Preparation of ethyl 3-phenylpropiolate (1-1a) 12
Scheme 9: Synthesis of Nitrosobenzene & List of Nitrosobenzene 12
Scheme 10: Formation of diazene oxide 17
Scheme 11: A plausible reaction mechanism 18

Chapter II

Scheme 1: Hydroamination reaction over alkyne 126
Scheme 2: A3 coupling Reaction 126
Scheme 3: Gold-catalyzed hydroamination Reaction 127
Scheme 4: A3 Coupling catalyzed by gold in water 128
Scheme 5: AA3 Coupling catalyzed by Copper in water and organic solvent 129
Scheme 6: Hydrative aldol reactions of 2-en-1-ynamides and aldehyde with water 129

Scheme 7: [4+2] cycloaddition between ynamides and imines 130
Scheme 8: Synthesis of N-methyl-1,4-dihydropyridines 131
Scheme 9: Synthesis of propargyl ethyl ethers by an A3-coupling-type reaction 132
Scheme 10: Catalytic functionalizations of alkynes with amines 133
Scheme 11: Preparation of 3-en-1-ynamide (2-1a) 136
Scheme 12: Synthesis of N-methyl-N-(3-methylenehept-1-yn-1-yl) methane 136
sulfonamide
Scheme 13: Reactions with cycloalkane-derived ynamides 142
Scheme 14: Chemical elaborations of products 142
Scheme 15: Rationales for the anti- and syn-Selectivity 144

Chapter III

Scheme 1: Formation of gold carbenes from diazo compounds 325
Scheme 2: General reactivity of ynamides in gold catalysis 326
Scheme 3: Au(I)-Catalyzed [3 + 2] Cycloaddition Vinyldiazoacetates & Enol Ethers 327
Scheme 4: [3 + 2] Cycloaddition of Nitriles with alkenyl diazo compounds 328
Scheme 5: Proposed Mechanisms for the Formal [3+3]-Cycloaddition 328
Scheme 6: Gold-catalyzed cyclopropanation and cyclopenetenation 329
Scheme 7: [3 + 2] Cycloaddition Reaction of Aryldiazoesters with Terminal Alky 330
Scheme 8: Rhodium-catalyzed C−H functionalization of diazo molecule 331
Scheme 9: Rhodium and copper-catalyzed tandem annulation 332
Scheme 10: General scheme with few useful reaction 334
Scheme 11: Preparation of ynamides 337

Scheme 12: Synthesis of 2-diazo-2-phenylacetonitrile 338
Scheme 13: gold-catalyzed annulation with meta substituted diazo compounds 341
Scheme 14: Additional reaction 342
Scheme 15: Gold-catalyzed cyclopropenation of internal yanmides 342
Scheme 16: Postulated mechanism for [3+2]-annulation reaction 343

Chapter IV

Scheme 1: Metal-mediated carbene transfer from diazo compounds. 495
Scheme 2: Ru-Catalyzed C2-Selective Functionalization of NH-Indole 497
with diazo acetates
Scheme 3: Mechanism of Iron(II)-Catalyzed Curtius-like Rearrangement 498
Scheme 4: Proposed Mechanisms for the construction of BIMs 499
Scheme 5: Plausible reaction pathway for the unsymmetric double arylation 500
of nitrodiazoesters
Scheme 6: Proposed mechanism for Synthesis of BIMs with alloxane 501
Scheme 7: Proposed mechanism of the iridium/iminium co-catalyzed 502
three-component reaction
Scheme 8: Concept of carbenoid functionalization with Diazo compounds 503
Scheme 9: Synthesis of N-methyl indole 507
Scheme 10: Synthesis of N-phenyl indole 507
Scheme 11: Synthesis of 2-diazo-2-phenylacetonitrile 507
Scheme 12: Proposed mechanism for Gold-Catalyzed Carbenoid 512
functionalization of indole


List of Tables

Chapter I

Table 1: Reactions over various catalysts 10
Table 2: Catalyst Reaction over various alkynes. 14
Table 3: Catalytic reactions with various nitrosoarenes 16

Chapter II

Table 1: Tests over various metal catalysts 134
Table 2: Reactions with various aldehydes and anilines 137
Table 3: Reactions with substituted 3-en-1-ynamides 140

Chapter III

Table 1: Catalyst reactions with various diazo species and catalysts 335
Table 2: [3+2]-Annulations with ynamides and diazonitriles 339

Chapter IV
Table 1: Catalyst reactions with various diazo species and catalysts 505
Table 2: Substrate scope for double nucleophilic addition reaction of 508
N-Methyl Indole and diazonitriles
Table 3: scope of reaction with various diazo nitrile 510
List of Figures
Chapter I
Figure 1: Singlet and triplet carbenes 2
Figure 2: Fischer and Schrock carbenes 3
Figure 3: List of Ethyl propiolate substrates 12
Figure 4: ORTEP diagram of 1-3j and 1-6a 19

Chapter II

Figure 1: List of 3-en-1-yanamide substrates 135
Figure 2: ORTEP diagram of 2-4k, 2-5e, 2-5i, 2-5k 146

Chapter III

Figure 1: List of yanmides substrates 336
Figure 2: List of diazo substrates 337
Figure 3: ORTEP diagram of 3-4a and 3-3a’ 344

Chapter IV

Figure 1: Classification of carbene precursors 496
Figure 2: List of alkaloids and bioactive molecules with BIM core structure 504
Figure 3: Indole substrate 506
Figure 4: List of diazo substrates 506
Figure 5: ORTEP diagram of 4-3j and 4-3p’ 513

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