利用銅的光氧化還原錯合物（λabs= 472nm）透過低能量的可見光來轉化末端炔類，以合成有價值的含官能團化合物。其中氧氣（O2）和苯醌（BQ）被當作電子受體，它們與三重激發態銅（I）—苯乙炔化物進行單電子轉移過程，以生成具反應性自由基，例如：超氧化物自由基陰離子和苯醌醌陰離子，以上皆可以由EPR來證明。與現有的昂貴的光催化方法（利用Ru，Ir，Rh的光氧化還原催化劑）相比，這些獨特的光氧化還原轉化反應是前所未有且便宜的。反應條件很簡單，避免使用強外部氧化劑和配體，就可以在室溫下反應而不會產生任何可能的不需要的副產物。本論文分成四章來描述了以下前所未有的關鍵特徵反應：（a）末端C≡C鍵的受控氧化，（b）連續的單電子轉移和氫原子轉移過程（HAT）來使未活化烷基的選擇性α-CH鍵活化醇形成α-氧基自由基，（c）末端炔烴的區域選擇性乙醯胺化，以及（d）使用簡單銅鹽和藍光LED當作催化劑在室溫下使末端炔類能夠形成新的CO，CN和CS鍵，這是現有的文獻方法無法實現的。往後可多樣化應用這些合成功能去製備各種生物活性化合物，來證明這些光氧化還原反應的合成效用。





第1章：銅的光氧化還原來合成α-酮酯、喹喔啉和萘醌：末端炔烴受控氧化成乙二醛


第2章：可見光驅動的銅光氧化還原催化的HAT過程來耦合芳胺、末端炔烴和醇類

第3章：可見光促進的銅催化將芳基胺和末端炔類區域選擇性的醯胺化

第4章：銅/ TMS-N3透過光氧化還原共催化末端炔類進行氧基磺醯化來形成碳—硫鍵

An in situ generated copper photoredox complex (λabs=472nm) was utilized for the transformation of terminal C≡C bonds to synthesize valuable functional group containing compounds using low energy visible light irradiation. Molecular oxygen (O2) and benzoquinone (BQ) were used as electron acceptors, which undergoes single electron transfer process with triplet excited Copper (I) Phenylacetylide to generate reactive radical species i.e., superoxide radical anion and benzoquinone radical anion respectively evidenced by EPR. These unique photoredox transformations are unprecedented and cheaper in contrast to the existing expensive photocatalytic approaches (Ru, Ir, Rh based photoredox catalysts). The reaction conditions are simple by evading the use of strong external oxidants, complex ligands and can be employed at room temperature without producing any possible unwanted side products. This thesis consisting of 4 chapters describing key unprecedented features as follows:(a) controlled oxidation of terminal C≡C bonds, (b) consecutive single electron transfer and hydrogen atom transfer process (HAT), selective α-C-H bond activation of unactivated alkylalcohols to form of α-oxy radical, (c) regioselective acetamidation of terminal alkynes, and (d) Oxy-Sulfonylation of terminal alkynes to enable new C-O, C-N, and C-S bond formations respectively under blue LED irradiation using simple copper salts as catalyst at room temperature which are not possible with existing thermal literature procedures. Late stage diversification was applied to these synthesized functionalities to prepare various biologically active compounds to demonstrate the synthetic utility of these photoredox protocols.
Chapter 1: Copper Catalyzed Photoredox Synthesis of α-Keto Esters, Quinoxaline, Naphthoquinone: Controlled Oxidation of Terminal Alkynes to Glyoxals
(Chem. Sci.,2018, 9, 7318–7326)

Chapter 2: Visible Light-driven Copper Photoredox-catalyzed Multicomponent Coupling of Arylamines, Terminal Alkynes, and Alcohols via HAT Process
(Angew. Chem. Int. Ed., 2019, 131, 3878–3882)



Chapter 3: Visible Light-promoted Copper Catalyzed Regioselective Acetamidation of Terminal Alkynes by Arylamines
(Green Chem., 2020, 22, 1164-1170)
Chapter 4: Copper/TMSN3 cocatalyzed Oxy-Sulfonylation of Terminal Alkynes via C-S Coupling Enabled by Photoredox Catalysis

論文摘要…………………………………...............................................I
Abstract…………………………………................................................IV
Acknowledgement…………………………………………………......VII
Contents…………………………………………………………...........X
List of Figures…………………………………………………………XV
List of Tables…………………………………………………….........XIX
List of Schemes………………………………………………………XXIII
List of Publications…………………………………………………XXIX
Abbreviations……………………………...........................................XXX


Chapter 1
Overview of the Dissertation
Copper Catalyzed Photoredox Synthesis of -Keto Esters, Quinoxaline, Naphthoquinone: Controlled Oxidation of Terminal Alkynes to Glyoxals
1.1 Introduction 1
1.2 Results and Discussion 5
1.3 Conclusion 21
1.4 Experimental section 21
1.4.1. General procedure for the formation of α-keto esters…. 22
1.4.2. General Procedure for competitive reaction 1o, 2o and 3o alcohols…....….23
1.4.3. Experimental procedure for biologically active compounds……………...24 1.4.4 Evaluation of Green metrics of the current photochemical process….....….29
1.4.5 Evaluation of Green metrics of the thermal literature process……...……...31 1.4.6 EPR measurements using spin trapping agent DMPO……………………..37 1.4.7 Isotopic labelling experiment…………………………………………........42
1.5 References…………………………………………………………...…………...67


Chapter 2

Visible Light-driven Copper Photoredox-catalyzed Multicomponent Coupling of Arylamines, Terminal Alkynes, and Alcohols via HAT Process
2.1 Introduction 72
2.2 Results and Discussion 75
2.3 Conclusion 85
2.4 Experimental section 86
2.4.1. General procedure 86
2.4.2. Preparative scale synthesis of propargylamine (3d) …......………………..87 2.4.3. Late stage diversification of propargylamines………………..…………...88 2.4.4 Kinetic Isotope Effects ……………………….…....................................…90
2.4.5 The intermolecular crossover experiment …..……………………………..92
2.4.6 Radical clock experiments………………………………...............………..93 2.4.7 IR-spectra of Copper(I) phenylacetylide …………………………...……...99 2.4.8 EPR measurements………………………………………………………..100
2.5 References…………………………………………………………...………….131




Chapter 3
Visible Light-promoted Copper Catalyzed Regioselective Acetamidation of Terminal Alkynes by Arylamines
3.1 Introduction ……………………………………………………...……………..…..136 3.2 Results and Discussion ……………………………………………...………….139
3.3 Conclusion…………………………………………………………….………...150
3.4 Experimental section……………………………………………………………151
3.4.1. General procedure………………………………………………………..152
3.4.2. Green metrics evaluation for photoredox method………………………..155 3.4.3. Evaluation of green metrics for thermal process……………………........157 3.4.4 EPR measurements......................................................................................163
3.4.5 Isotopic labelling experiments …………………………………………...166 3.5 References………………………………………………...…………………….199





Chapter 4
Copper/TMSN3 cocatalyzed Oxy-Sulfonylation of Terminal Alkynes via C-S Coupling Enabled by Photoredox Catalysis
4.1 Introduction ………………………………………………………...…………..202
4.2 Results and Discussion ……………………………………………...………….205
4.3 Conclusion…………………………………………………………….………...213
4.4 Experimental section……………………………………………………………214
4.4.1. General procedure to synthesize β-keto sulfone……………………..….215
4.4.2. Optical pictures of the reaction mixture ………………..………….……216
4.4.3. Synthetic comparison of 4q .………… ……………….…………….….217 4.4.4 Green Metrics evaluation for synthesizing 4q...........................................218
4.4.5 Comparison of mechanistic pathways..…………………………….….....220 4.4.6 Preparation of copper(I) phenylacetylide………………..……………….221 4.4.7 EPR measurements:……………………....…………………...…………221
4.4.8 Excitation and emission spectra of copper(I)-phenylacetylide…….….....224
4.4.9 18O2labeling experiment:…………………..…………..………................225
4.5. References……………………..…………………………………….................239

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Mei-Lin Feng,
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