本篇論文討論了利用金和銀所組成的催化劑建立新穎的有機轉化。通過使用這些金屬，可以使用 較為溫和及具選擇性且更加有效的方式從容易獲得之反應物中生成各種具有合成價值的複雜有機 化合物。為了使本論文更易於理解，分為三個章節。
第一章是使用P(t-Bu)2(o-biphenyl)Au 催化劑催化炔丙醇與硝酮的金催化之氧化反應，從金烯醇鹽 的曼尼希反應中得到雙環環化產物。使用相同的金催化劑，可以讓使用相同的炔丙基胺與硝酮反 應產生不同的氧代芳香基產物。根據我們的DFT 計算表明，使用多電子金催化劑將炔丙醇與硝酮 氧化僅會產生金碳烯，其可以生成金烯醇化合物或氧代芳香基的中間產物，其中烯醇鹽的障壁小 於氧代芳香基化合物。
第二章介紹了以立體選擇性的金催化重氮吲哚酮和1,2,4-取代二烯合成螺環環丙基吲哚酮。這項工 作的目的是用金催化劑對這些螺環環丙基吲哚酮進行新的重排生成3- (環戊-1,3-二烯-1-甲基) 吲哚 酮。由實驗數據可以排除金催化環丙烷化中的可逆過程。通過DFT 計算，我們假設重排機制牽涉 到形成複雜的金烯醇鹽和1-亞甲基-2,3,4-環戊二烯基陽離子，導致1,5-烯醇鹽移位。
第三章由 α-重氮酯和α-芳基重氮酮的交叉偶聯實現了3(2H)-呋喃酮衍生物的無催化劑合成。透過 Wolff 重排 α-芳香基重氮酮類熱分解得到酮烯，該重排與α-重氮酯反應通過分子間重氮交聯耦合 形成3(2H)-呋喃酮衍生物。這是一種有效合成具四元立體中心生物活性的3(2H)-呋喃酮衍生物的方法。

This dissertation discussed the creation of novel synthetic organic transformations utilizing catalysts made of gold and silver. By using these metals, it is possible to create a variety of synthetically valuable complex organic compounds out of easily available substrates in a mild, selective, and efficient manner. In order to make this
dissertation easier to understand, it is divided into three chapters.
Chapter one is comprised of gold catalyzed oxidations of propargyl alcohols with nitrones using P(t-Bu)2(o-biphenyl)Au+catalyst, afforded bicyclic annulation products from the Mannich reactions of gold enolates. The same reactions of propargylamines with nitrones using the same gold catalyst gave distinct oxoarylation products. Our DFT calculations indicate that oxidation of propargyl alcohols with nitrones using electron-rich gold catalysts lead only to gold arbenes, which can generate gold enolates or oxoarylation intermediates with enolate species having a barrier smaller than that of oxoarylation species.
Chapter two is comprised of gold-catalyzed stereoselective synthesis of spirocyclopropyl oxindoles from diazooxindoles and 1,2,4-substituted dienes is described. The aim of this work is to report a novel rearrangement of these spirocyclopropyl oxindoles with gold catalyst to yield 3-(cyclopenta-1,3-dien-1-ylmethyl)oxindoles. Our experimental data exclude a reversible process in the gold-catalyzed cyclopropanation. With DFT-calculations, we postulate a rearrangement
mechanism involving the formation of complex pairs of gold enolates and 1-methylen-2,3,4-cyclopentadienyl cations, leading to a 1,5-enolate shift.
Chapter three is comprised of catalyst-free synthesis of 3(2H)-furanone derivatives has been achieved from cross-coupling of α-diazo ester and α-aryldiazo ketones are described. Thermal decomposition of α-aryldiazo ketones gives ketene through Wolff rearrangement which reacts with the α-diazo ester to form 3(2H)-furanone derivatives via intermolecular diazo-cross coupling. This is a useful method for the synthesis of biological active 3(2H)-furanone derivatives, containing a quaternary stereocenter is described.

TABLE OF CONTENTS
Abstract I
Acknowledgment IV
Table of content VI
List of Schemes IX
List of Tables XI
List of Figures XI
List of Publications XIII
Abbreviations XIV

Chapter 1: Gold-Catalyzed Oxidative Aminocyclizations of Propargyl
Alcohols and Propargyl Amines to Form Two Distinct Azacyclic Products:
Carbene Formation versus a 3, 3-Sigmatropic Shift of an Initial Intermediate.
Introduction 02
Result and Discussion 13
Conclusion 31
Experimental Procedure 32
Spectral Data 37
X-ray Crystallographic Data 61
References 69
1H and 13C NMR Spectra 72

Chapter 2: Gold-Catalyzed Rearrangement of α-Carbonyl Cyclopropanes to Form 3-(Cyclopenta-1,3-dien-1-ylmethyl)oxindoles via a Postulated 1,5-Enolate Shift
Introduction 178
Result and Discussion 190
Conclusion 208
Experimental Procedure 208
Spectral Data 219
References 242
X-ray Crystallographic Data 245
1H and 13C NMR Spectra 253

Chapter 3: Catalyst Free Diazo Cross-coupling to Synthesis Biological Active 3(2H)-Furanone derivatives
Introduction 352
Result and Discussion 363
Conclusion 377
Experimental Procedure 378
Spectral Data 385
References 400
X-ray Crystallographic Data 403
1H and 13C NMR Spectra 414

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