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Iron-Catalyzed Oxidation in Metal Organic Frameworks

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Iron-Catalyzed Oxidation in Metal Organic Frameworks Iron-Catalyzed Oxidation in Metal Organic Frameworks Thesis by Raymond John Strobel In Partial Fulfillment of the Requirements For the Degree of Bachelor of Science in Chemistry University of Michigan Ann Arbor, Michigan 2014 Thesis Advisor: Professor Melanie Sanford DEDICATION To my mother and father, Susan and Stephen Strobel, for their unconditional love and support -- And -- To Dr. Doug Genna, for his invaluable mentorship, guidance, and friendship. i ACKNOWLEDGMENTS I thank Professor Melanie Sanford for investing so much of her time and energy in my growth as an aspiring research scientist. Belonging to and working in your laboratory has been the single greatest honor of my undergraduate career at Michigan; what a thrill it was to be mentored by a MacArthur fellow (and a fellow Rhode Island native at that)! Your leadership as a principle investigator continues to inspire and impress me. You empower your students to realize their full potential, and take a genuine interest in their personal well-being. The unwavering passion you have for your chemistry, and for conducting research of the highest standards, is contagious. As a student in your lab, you gave me a high reputation to live up to. In my moments of weakness, you found opportunities for growth, not condemnation. As I begin my new journey as an aspiring physician-scientist, I look to your example for guidance. I wish you and your family the best of health and happiness in the years to come! Ralph Waldo Emerson wrote that, “Our chief want in life, is, somebody who shall make us do what we can. This is the service of a friend. With him we are easily great.” What an apt description of you, Dr. Genna. As my mentor you empower me to do what I can, and more. In your honest way, you encouraged me to settle for nothing short of excellence, and provided me with tangible goals for improvement. In the lab, we shared laughter and frustration. You taught me to chase success, rather than shy from failure. I have watched as you simultaneously navigated your post-doctoral research and the responsibilities of fatherhood: I am still not sure how you manage it! May you find success and happiness with your family in Youngstown, OH. Lastly, thanks go out to BJ, Nomaan, Nicole, Ansis, Dr. Monica Perez-Temprano, and Dr. Rebecca Loy for sharing in my undergraduate research experience with me. ii TABLE OF CONTENTS DEDICATION………………………………………………………………………………...........i ACKNOWLEDGEMENTS…………………………………………………………………….….ii LIST OF SCHEMES…………………………………………………………………………….....v LIST OF FIGURES…………………………………………………………………………….....vii LIST OF TABLES……………………………………………………………………………….viii ABSTRACT……………………………………………………………………………………….ix Chapter 1: Introduction ……………………………………………………………………...1 1.1 Iron: An Ideal Transition Metal Catalyst……………………………………...1 1.2 Iron Catalyzed Carbene C-H Insertions…………............................………….2 1.3 Iron Catalyzed C-H Functionalization…………............……………………...3 1.4 Iron Catalyzed Alkene Oxidation…………………………………………......7 1.5 Shortcomings of Iron Heme and Non-Heme Catalysis……………………....10 1.6 Catalytically Active Metal Organic Frameworks...........................…….........10 1.7 References……………………………………………………...…………….15 Chapter 2: Iron Catalyzed Carbene C-H Insertion.............................................................18 2.1 Introduction………………………........……………………….….………...18 2.2 Results and Discussion…….........................………………….....…….….…18 2.3 Conclusion.......................................................................................................25 2.4 Experimental Procedures and Characterization Data......................................25 2.5 References.......................................................................................................27 iii Chapter 3: Iron Catalyzed C-H Functionalization 3.1 Introduction………………………………………………………....…..........29 3.2 Results and Discussion....................................................................................31 3.3 Conclusion.......................................................................................................38 3.4 Experimental Procedures and Characterization Data......................................38 3.5 References.......................................................................................................39 Chapter 4: Iron Catalyzed Alkene Oxidation 4.1 Introduction.....................................................................................................41 4.2 Results and Discussion....................................................................................42 4.3 Conclusion.......................................................................................................50 4.4 Experimental Procedures and Characterization Data......................................50 4.5 References.......................................................................................................52 iv LIST OF SCHEMES CHAPTER 1: Introduction Scheme 1.2.1. Fe(TPP)Cl Catalyzed C-H Insertion with Ethyl Diazoacetate…………………….3 Scheme 1.2.2. Fe(TPP)Cl Catalyzed C-H Insertion with p-methoxy methyl 2-phenyldiazoacetate………………………………………………………………………………3 Scheme 1.3.1. Oxidation of Aliphatic Bonds in Cyclohexane…………………………...……….4 Scheme 1.3.2. Asymmetric Hydroxylation of Ethylbenzene……………...……………………...5 Scheme 1.3.3. Selective Aliphatic C-H Oxidation using Fe(PDP) (4)……………………………7 Scheme 1.4.1. Epoxidation Catalyzed by Fe(TPP)Cl……………………………………………..8 Scheme 1.4.2 Oxidation of Cyclooctene with Fe(TPA…………………………...…….…...……9 Me,H Scheme 1.4.3 Oxidation of Cyclooctene with [Fe(CF3SO3)2( PyTACN)…..………..…..…...9 Scheme 1.6.1. C-H and Alkene Oxidation Catalyzed by PIZA-3………………………..…...…11 Scheme 1.6.2 C-H Oxidation Catalyzed by ZJU-18……………………………………..….…..12 Scheme 1.6.3. Oxidation of Ethylbenzene via ZJU Fe- and Mn-TCCP MOFs…………......…..12 Scheme 1.6.4. Ion-Exchange Encapsulation of Catalyst in MOF…………………..……....…...14 CHAPTER 2: Iron Catalyzed Carbene C-H Insertion Scheme 2.2.1. Synthesis of Porph@MOM-4................................................................................19 Scheme 2.2.2. Synthesis of FeZn RPM.........................................................................................20 Scheme 2.2.3. M-Porphyrin @ MOF-5 Synthesis........................................................................21 Scheme 2.2.4. Homogeneous Fe[OEP]Cl Carbene C-H Insertion................................................22 CHAPTER 3: Iron Catalyzed C-H Functionalization Scheme 3.1.1. Regioselective C-H Functionalization by 1...........................................................30 Scheme 3.2.1. Doping of ZJU-28 with Fe(S,S-PDP (1))...............................................................34 v CHAPTER 4: Iron Catalyzed Alkene Oxidation Me,H Scheme 4.1.1. Oxidation of Cyclooctene with [Fe(CF3SO3)2( PyTACN)] (1)........................41 Scheme 4.1.2. Proposed Over-oxidation of Styrene Oxide to Benzaldehyde...............................42 vi LIST OF FIGURES CHAPTER 1: Introduction Figure 1.1.1. Non-Heme (H2-(S,S-PDP), 1) and Heme (H2TPP, 2) Ligands……………………..2 Figure 1.3.1. Bimolecular µ-oxo Iron Porphyrin Decomposition Product……..………………...5 Figure 1.6.1. [Mn5Cl2(MnCl-OCPP)(DMF)4(H2O)4 ]·2DMF·8CH3COOH·14H2O……………11 CHAPTER 2: Iron Catalyzed Carbene C-H Insertion Figure 2.2.1. Cubic MOF-5...........................................................................................................21 CHAPTER 3: Iron Catalyzed C-H Functionalization Figure 3.1.1. Important Compounds Containing Hydroxyl and Carbonyl Units..........................29 Figure 3.1.2. [Fe(S,S-PDP)(CH3CN)2] (SbF6)2 (1).......................................................................30 Figure 3.2.1. Structure of ZJU-28.................................................................................................33 Figure 3.2.2. Initial Heterogeneous C-H Functionalization Trials...............................................34 Figure 3.2.3. Heterogeneous Reactions Utilizing Neat Reaction Conditions...............................36 Figure 3.2.4. Determination of Role of AcOH in C-H Functionalization....................................37 CHAPTER 4: Iron Catalyzed Alkene Oxidation Figure 4.2.1. Fe(S,S-PDP) (1) and Fe(TPA) (2)............................................................................43 Figure 4.2.2. PCN-222(Fe) (3) and Fe(III)Cl-H4TCPP (4)...........................................................48 vii LIST OF TABLES CHAPTER 1: Introduction CHAPTER 2: Iron Catalyzed Carbene C-H Insertion Table 2.2.1. Fe[OEP]Cl @ MOF-5 Temperature Trials...............................................................22 Table 2.2.2. Fe[OEP]Cl Substrate Screen.....................................................................................23 Table 2.2.3. Fe[OEP]Cl @ MOF-5 Recycle and Filtrate Tests....................................................24 Table 2.2.4. Fe[OEP]Cl @ MOF-5 Recycle and Filtrate Tests....................................................25 CHAPTER 3: Iron Catalyzed C-H Functionalization Table 3.2.1. Replication of Literature Data for Fe(S,S-PDP)........................................................32 CHAPTER 4: Iron Catalyzed Alkene Oxidation Table 4.2.1. Homogeneous Fe(S,S-PDP) and Fe(TPA) Styrene Oxidation Trials...........................43 Table 4.2.2. Heterogeneous Fe(S,S-PDP)/ZJU-28 Replication of Homogeneous Styrene Oxidation Trials.............................................................................................................................45
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