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Synthetic and Mechanistic Studies of Ruthenium Catalyzed C-C and C-O Bond Activation Reactions

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Synthetic and Mechanistic Studies of Ruthenium Catalyzed C-C and C-O Bond Activation Reactions Marquette University e-Publications@Marquette Dissertations, Theses, and Professional Dissertations (1934 -) Projects Synthetic and Mechanistic Studies of Ruthenium Catalyzed C-C and C-O Bond Activation Reactions Junghwa Kim Marquette University Follow this and additional works at: https://epublications.marquette.edu/dissertations_mu Part of the Chemistry Commons Recommended Citation Kim, Junghwa, "Synthetic and Mechanistic Studies of Ruthenium Catalyzed C-C and C-O Bond Activation Reactions" (2016). Dissertations (1934 -). 1001. https://epublications.marquette.edu/dissertations_mu/1001 SYNTHETIC AND MECHANISTIC STUDIES OF RUTHENIUM CATALYZED C-C AND C-O BOND ACTIVATION REACTIONS By Junghwa Kim, B.Sc. M.Sc. A Dissertation Submitted to the Faculty of the Graduate School, Marquette University, in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy Milwaukee, Wisconsin May 2016 ABSTRACT SYNTHETIC AND MECHANISTIC STUDIES OF RUTHENIUM CATALYZED C-H and C-O BOND ACTIVATION REACTIONS Junghwa Kim, B.Sc. M.Sc. Marquette University, 2016 Etherification of alcohols is one of the most fundamental transformations in organic synthesis. Williamson ether synthesis is the most well-known synthetic method of unsymmetrical ether synthesis which is still being used in both industrial and academic laboratories. We have developed a novel catalytic etherification reaction using two different alcohols by using a well-defined cationic ruthenium catalyst. The reaction scope as well as the mechanistic study of the reaction are described. Hydroacylation is considered to be a powerful synthetic transformation for producing functionalized ketones from relatively simple olefin substrates. Despite remarkable progress in intra and intermolecular hydroacylations, the substrate scope of the reaction was limited to chelate assisted aldehydes and alkenes. We developed a highly regioselective intermolecular hydroacylation by using a well-defined cationic ruthenium catalyst. The reaction scope as well as the mechanistic study of the reaction are described. Transition metal catalyzed C(sp3)-H bond activation is highly challenging but very important in a number of catalytic reforming processes in the petroleum industries. Tandem reactions are a powerful strategy due to the reduction of work-up procedures and multiple purification steps. We developed a novel tandem catalytic reaction involving C(sp3)-H bond activation and functionalization by using a well-defined tetra ruthenium catalyst. The scope and synthetic utility of the tandem dehydrogenation-alkylation reaction are described. i ACKNOWLEDGMENTS I would like to thank to my Ph.D. advisor, Professors Chae Sung Yi, for his support during the past five years. I would like to thank you for encouraging my projects to be completed and for allowing me to become an independent research scientist. Your advice and guideline on both research as well as on my career are precious. I would also like to thank my committee members, Professors Adam Fiedler, Christopher Dockendoff, and Mark G. Steinmetz for insightful comments and guidance. I would like to thank my group members, Hanbin Lee, Nuwan Pannilawithana, Kirindearachchi Pandula, and former group members as mentors, Dr. Dong-Hwan Lee, Dr. Ki-Hyeok Kwon, and Dr. Kwang- Min Choi for their valuable conversations and guidance. I am deeply grateful to my mother-in-law, father-in-law, my mother, and father for their patience, sacrifice, and prayer. Specially, I would like express the deepest love to my wife, Dami Kim, who spent sleepless nights with me for any hardship. ii TABLE OF CONTENTS ACKNOWLEDGMENTS……………………………………………………………...….i TABLE OF CONTENTS…………………………………………………………………ii LIST OF TABLES………………………………………………………………….……vii LIST OF FIGURES………………………………………………………………………ix LIST OF SCHEMES…………………………………………………………………...…x 1 Unsymmetrical Etherification Reactions ........................................................................... 1 1.1 Williamson Ether Synthesis ................................................................................. 1 1.2 Modifications of Williamson Ether Synthesis ..................................................... 3 1.2.1 Using Weak Alkylation Agents .....................................................................3 1.2.2 Ullmann Condensation...................................................................................5 1.3 Catalytic Etherification Methods ......................................................................... 7 1.3.1 Rhenium Catalyzed Methods .........................................................................7 1.3.2 Reduction of Esters with InBr3 Catalyst ......................................................10 1.3.3 Etherification by [IrCl2Cp*(NHC)] Catalyst ...............................................12 1.4 Other Etherificaiton Reactions ........................................................................... 15 1.4.1 Mitsunobu Etherification .............................................................................15 1.4.2 Modified of Mitsunobu Reaction .................................................................16 1.4.3 Etherification by using Dialkylphosphites ...................................................18 1.4.4 Etherification by Addition of Alcohols to Alkenes .....................................19 1.4.5 Etherification by Using BiBr3 ......................................................................21 1.4.6 Etherification by Using Perfluoroimidates ..................................................24 iii 1.4.7 Dehydrative Coupling of Alcohols by Sodium Bisulfite .............................26 1.4.8 Etherification by Palladium Catalyst ...........................................................28 2 Introduction of Synthesis of Unsymmetrical Ethers from the Ruthenium (II) Catalyzed Dehydrative Coupling of Alcohols ......................................................................... 30 2.1 Result and Discussion ........................................................................................ 30 2.2 Optimization Studies .......................................................................................... 34 2.2.1 Catalyst Screening .......................................................................................34 2.2.2 Solvent and Temperature Effects .................................................................36 2.2.3 Optimization of Turnover Number (TON) and Turnover Frequency (TOF) ......................................................................................................................37 2.3 Reaction Scope ................................................................................................... 38 2.3.1 Synthesis of Unsymmetrical Ethers from the Dehydrative Coupling of Alcohols ......................................................................................................................38 2.3.2 Synthesis of Bioactive Unsymmetrical Ethers .............................................42 2.3.3 Stereochemical and X-ray Crystallographic Determination of the Unsymmetrical Ethers………… ............................................................................... 46 2.4 Mechanistic Studies............................................................................................ 49 2.4.1 Determination of the Stereochemistry of Unsymmetrical Ethers ................49 2.4.2 Hammett Study ............................................................................................53 2.4.3 H/D Exchange Experiment ..........................................................................56 2.4.4 Carbon Isotopes Effect .................................................................................57 2.5 Proposed Mechanism ......................................................................................... 60 2.6 Conclusions ........................................................................................................ 62 3 Introduction Hydroacylation Reaction with Transition Metal Catalysts ..................... 63 3.1 Intramolecular Hydroacylation of alkenes ......................................................... 65 3.2 Intermolecular Hydroacylation of alkenes ......................................................... 66 iv 3.3 Markovnikov Selective Intermolecular Hydroacylation of Alkenes .................. 70 3.3.1 Hydroacylation with Salicylic Aldehydes and Dienes .................................70 3.3.2 Hydroacylation of Salicylic Aldehyde and Homoallylic Sulfides or Homoallylic Alcohols………… .................................................................................75 3.3.3 Hydroacylation of Nonchelating Aldehydes with Enones or Dienes ..........77 3.3.4 Hydroacylation with Nonchelating Aldehydes with 1-Vinylphenol ...........80 3.3.5 Current Issues and Challenges .....................................................................83 4 Intermolecular Markovnikov-Selective Hydroacylation of Olefins Catalyzed by a Cationic Ruthenium-Hydride Complex.................................................................................... 84 4.1 Introduction ........................................................................................................ 84 4.2 Results and Discussion ....................................................................................... 85 4.3 Optimization Studies .......................................................................................... 88 4.3.1 Solvent and Temperature Effects .................................................................88
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