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Oxygen Bond Activation 1 Development of Nickel-Catalyzed Methods for Deoxygenation Processes by David P. Todd A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy (Chemistry) in the University of Michigan 2017 Doctoral Committee: Professor John Montgomery, Chair Professor Rudy Richardson Professor Melanie Sanford Professor John Wolfe Dedication I dedicate this dissertation to my family, Paul, Rose and Laura, and to Jessica. ii Acknowledgements I would like to thank my advisor John Montgomery for his guidance and mentorship. Under his supervision, I have learned to be a more creative thinker and a dedicated researcher. I would also like to thank my dissertation committee for all of their helpful comments and advice. I would also like to thank the members of the Montgomery Lab past and present who have helped me during my time in the group. Through my interactions and discussions with them, I have as a chemist, and they have helped make graduate school a more enjoyable experience. Eric Wiensch is acknowledged for his collaborative work in the developments described in Chapter 3 of my thesis. Lastly, I would like to thank my family, friends, and my girlfriend Jessica for their support throughout my graduate career. iii Table of Contents Dedication ii Acknowledgements iii List of Schemes vii List of Tables xi Abbreviations xii Abstract xv Chapter 1 Introduction to Nickel-Catalyzed Carbon(sp2)-Oxygen Bond Activation 1 1.1 Introduction to Carbon(sp2)-Oxygen Bond Cleavage 1 1.2 Advantages of Nickel Catalysts towards Carbon(sp2)-Oxygen Bond Cleavage 4 1.3 Nickel-Catalyzed Carbon(sp2)-Oxygen Bond Cleavage Background 7 1.4 Statement of Thesis Content and Scope 9 Chapter 2 Deoxygenative C-C Bond-Forming Processes via a Net Four-Electron Reductive Coupling 11 2.1 Synthesis of 1,4-Dienes 11 2.2 Net Four-Electron Reductive Couplings 14 2.3 Optimization of Reaction Conditions 16 2.4 Mechanistic Considerations 20 2.5 Substrate Scope 26 2.6 Future Directions 27 iv 2.7 Summary of Net Four-Electron Reductive Coupling 29 Chapter 3 Nickel-Catalyzed Functionalization of Silyl Aryl Ethers 30 3.1 Introduction to Silyl-Protecting Groups 30 3.1.1 Nickel-Catalyzed Functionalization of Silyl Aryl Ethers 31 3.2 Introduction to Nickel-Catalyzed Reduction of Carbon(sp2)-Oxygen Bonds 32 3.2.1 Existing Methods for the Nickel-Catalyzed Reduction of Carbon(sp2)- Oxygen Bonds 33 3.2.2 Optimizations of Reaction Conditions 35 3.2.3 Mechanistic Investigations 42 3.2.4 Substrate Scope 46 3.2.5 Future Work 47 3.2.6 Summary of Reduction of Silyl Aryl Ethers 49 3.3 Introduction to Metal-Catalyzed Silylation of Carbon(sp2)-O Bonds 49 3.3.1 Existing Methods for the Metal-Catalyzed Silylation of Carbon(sp2)-O Bonds 50 3.3.2 Optimization of Reaction Conditions 51 3.3.3 Mechanistic Considerations 57 3.3.4 Substrate Scope 61 3.3.5 Future Work 64 3.3.6 Summary of Silylation of Silyl Aryl Ethers 66 3.4 Introduction to Nickel-Catalyzed Amination of Carbon(sp2)-Oxygen Bonds 66 3.4.1 Existing Methods for the Nickel-Catalyzed Amination of Carbon(sp2)- Oxygen Bonds 67 v 3.4.2 Optimization of Reaction Conditions 68 3.4.3 Reaction Mechanism 70 3.4.4 Substrate Scope 71 3.4.5 Future Directions 72 3.4.6 Summary 73 Chapter 4 Conclusion 75 4.1 Conclusion to Methodologies Towards the Deoxygenation of Small Molecules 75 Chapter 5 Experimental 79 5.1 General Experimental Details 79 5.2 Chapter 2 Experimental 80 5.2.1 General Procedure 80 5.2.2 Scheme 2.12 Substrate Scopes 84 5.2.3 Scheme 2.18 Deuterium Labeling Studies 94 5.3 Chapter 3 Experimental 97 5.3.1 General Procedures 97 5.3.2 Scheme 3.17 Substrate Scope for Reduction of Silyl Aryl Ethers 109 5.3.3 Scheme 3.29 Silylation Substrate Scope 118 5.3.4 Scheme 3.30 Scope of the Silanes in the Silylation Reaction 130 5.3.5 Scheme 3.38 Amination Substrate Scope 132 References 170 vi List of Schemes Scheme 1.1 Metal-Catalyzed Cross-Coupling Reactions 1 Scheme 1.2 Orthogonal Reactivity 2 Scheme 1.3 Initial C-O Cleavage 2 Scheme 1.4 Meyer Activation of Aryl Methyl Ethers 3 Scheme 1.5 Commonly Employed Protecting Groups 4 Scheme 1.6 Triflates Used in Palladium Cross-Coupling Reactions 5 Scheme 1.7 Limitations using Palladium 6 Scheme 1.8 Wenkert Discovery 8 Scheme 1.9 Dankwardt’s Modified System 8 Scheme 1.10 Scope of Transformations 9 Scheme 2.1 Natural Products Containing a 1,4-Diene 11 Scheme 2.2 Wilson 1,4-Diene Synthesis 12 Scheme 2.3 Trost 1,4-Diene Synthesis 12 Scheme 2.4 Micalizio 1,4-Diene Synthesis 13 Scheme 2.5 Coupling of Dienes and Terminal Olefins 13 Scheme 2.6 Net Neutral Couplings 14 Scheme 2.7 Two-Electron Reductive Couplings 15 Scheme 2.8 Net Four-Electron Reductive Couplings 16 Scheme 2.9 Formation of Z-Enol Silanes from Enals and Alkynes 16 Scheme 2.10 Initial Findings for 1,4-Diene Formation 17 vii Scheme 2.11 Synthesis of the Discrete ITol Catalyst 18 Scheme 2.12 Formation of Z-Enol Silanes from Enals and Alkynes 20 Scheme 2.13 C-O Reduction Mechanism 21 Scheme 2.14 Chatani Reduction of Aryl Pivalates 21 Scheme 2.15 Evaluation of Enol Silane for Productive 1,4-Diene Formation 22 Scheme 2.16 Mechanism Involving Formation of an Allylic Alcohol 23 Scheme 2.17 Evaluation of Allylic Alcohol in Proposed Mechanism 23 Scheme 2.18 Deuterium Labeling Studies 24 Scheme 2.19 Proposed Reaction Mechanism 25 Scheme 2.20 Substrate Scope 27 Scheme 2.21 New Reductive Couplings 28 Scheme 3.1 Installation and Removal of a Silyl Protecting Group 30 Scheme 3.2 Relative Stability of Silyl Protecting Groups 31 Scheme 3.3 Silyl Aryl Ethers as Cross-Coupling Partners 31 Scheme 3.4 Kumada Couplings Utilizing Silyl Aryl Ethers 32 Scheme 3.5 Ortho-metalation of Phenol Derivatives 32 Scheme 3.6 Reduction of Lignin Models 33 Scheme 3.7 Martin Reduction Method 33 Scheme 3.8 Hartwig Reduction Method 34 Scheme 3.9 Chatani Reduction 34 Scheme 3.10 Role of Titanium Lewis Acid in Synthesis of 1,4-Dienes 35 Scheme 3.11 Proposed Reduction of Silyl Enol Ethers 36 Scheme 3.12 Initial Reduction Findings 37 viii Scheme 3.13 Optimized Reduction Reaction Conditions 38 Scheme 3.14 Deuterium Labeling Study 42 Scheme 3.15 Proposed Reaction Mechanism 44 Scheme 3.16 Wu Computational Study of the Reduction of Phenyl Ethers 45 Scheme 3.17 Substrate Scope for Reduction of Silyl Aryl Ethers 47 Scheme 3.18 Proposed Reduction of Silyl Enol Ethers 48 Scheme 3.19 Modulation of the NHC Ligand 48 Scheme 3.20 One Pot Reduction of Phenols 49 Scheme 3.21 Hiyama-Denmark Cross-Coupling 50 Scheme 3.22 Martin Silylation of Aryl Pivalates 50 Scheme 3.23 Initial Discovery of Silylation 51 Scheme 3.24 Silanes as Reductants 52 Scheme 3.25 Optimized Reactions Conditions 53 Scheme 3.26 Proposed Silylation Mechanism 57 Scheme 3.27 Computational Insight into the Probable Reaction Mechanism 60 Scheme 3.28 Proposed Mechanism of the α-Bond Metathesis of the Silane 61 Scheme 3.29 Silylation Substrate Scope 63 Scheme 3.30 Scope of the Silanes in the Silylation Reaction 64 Scheme 3.31 Formation of Vinyl Silyl Ethers 65 Scheme 3.32 One Pot Reduction of Phenols 65 Scheme 3.33 Application of the Buchwald-Hartwig Method to Synthesis 67 Scheme 3.4 Amination of Aryl Methyl Ethers 68 Scheme 3.35 Amination of N-heteroaryl Methyl Ethers 68 ix Scheme 3.36 Optimized Reaction Conditions 69 Scheme 3.37 Proposed Amination Mechanism 71 Scheme 3.38 Amination Substrate Scope 72 Scheme 3.39 Ligand Framework 73 Scheme 3.40 Suzuki Reactions with Aryl Silyl Ethers 73 Scheme 4.1 Nickel-Catalyzed Functionalization of Phenol Derivatives 75 Scheme 4.2 Initial Net Four-Electron Discovery 76 Scheme 4.3 Functionalization of Silyl Aryl Ethers 76 x List of Tables Table 1.1 Nickel and Palladium Bond Activations 7 Table 2.1 Ligand Screen 18 Table 2.2 Evaluation of Discrete Catalyst 19 Table 2.3 Optimization using Discrete Catalyst 20 Table 2.4 Poor Reactivity of ITol 28 Table 3.1 Optimization of Catalyst and Reaction Time 38 Table 3.2 Optimization of the Ligand for Reduction 39 Table 3.3 Optimization of Reduction Protecting Group 40 Table 3.4 Optimization of Base Screen 40 Table 3.5 Lewis Acid Screening for Reduction 42 Table 3.6 Catalyst Optimization 53 Table 3.7 Optimization of the Ligand 54 Table 3.8 Optimization of Bases 55 Table 3.9 Optimization of the Protecting Group 56 Table 3.10 Amination Optimization 69 xi Abbreviations Ac acetyl acac acetylacetone Ar 1,3-Bis(1-adamantyl)imidazole-2-ylidene I(2-Ad) aryl BINAP (±)-2,2′-Bis(diphenylphosphino)-1,1′-binaphthalene tBu tert-butyl °C degrees Celsius COD cyclooctadiene Cy cyclohexyl Cp cyclopentadienly DMF dimethylformamide IPrMe 4,5-dimethyl-1,3-bis(2,4,6-triisopropylphenyl)-4,5-dihydro-imidazolium ee enantiomeric excess equiv equivalent Et ethyl nhex hexyl hr hour(s) IMes 1,3-bis-(1,3,5-trimethylphenyl)imidazol-2-ylidene IPr 1,3-bis-(2,6-diisopropylphenyl)imidazol-2-ylidene IPr*OMe N,N'-Bis(2,6-bis(diphenylmethyl)-4-methoxyphenyl)imidazol-2-ylidene xii IPrBAC N1,N1,N2,N2-tetraisopropylcycloprop-1-ene-1,2-diamine ITol 1,3-bis-(4-methylphenyl)imidazol-2-ylidene Me methyl MMA methyl methacrylate Mes mesityl min minute(s) MS molecular sieves NHC N-heterocyclic carbene nOct octyl PG protecting-group Ph phenyl Pin pinacol Piv pivalate iPr isopropyl nPr pentyl rt room temperature SIPr 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydro-imidazolium TBS tert-butyldimethylsilyl TMDSO 1,1,3,3-tetramethyldisilyloxane TBDPS tert-butyldiphenylsilyl TES triethylsilyl TESH triethylsilane Tf triflate xiii THF tetrahydrofuran tAm tert-amyl TBAF tetra-n-butylammonium fluoride PhMe toluene TIPS triisopropylsilyl TIPSH triisopropylsilane TMS trimethylsilyl xiv Abstract A new method for the reductive coupling of enals or enones and alkynes has been developed.
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