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Synthesis and Characterization of Chiral Oxovanadyl (Iv)

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Synthesis and Characterization of Chiral Oxovanadyl (Iv) SYNTHESIS AND CHARACTERIZATION OF CHIRAL OXOVANADYL (IV)- SALEN CATALYSTS AND VANADIUM-CATALYZED STEREOSELECTIVE EPOXIDATION REACTIONS A Thesis Presented to the faculty of the Department of Chemistry California State University, Sacramento Submitted in partial satisfaction of the requirements for the degree of MASTER OF SCIENCE in Chemistry by Diana Cheng SUMMER 2018 © 2018 Diana Cheng ALL RIGHTS RESERVED ii SYNTHESIS AND CHARACTERIZATION OF CHIRAL OXOVANADYL (IV)- SALEN CATALYSTS AND VANADIUM-CATALYZED STEREOSELECTIVE EPOXIDATION REACTIONS A Thesis by Diana Cheng Approved by: __________________________________, Committee Chair James Miranda, Ph.D. __________________________________, Second Reader Cynthia Kellen-Yuen, Ph.D. __________________________________, Third Reader Jacqueline Houston, Ph.D. ____________________________ Date iii Student: Diana Cheng I certify that this student has met the requirements for format contained in the University format manual, and that this thesis is suitable for shelving in the Library and credit is to be awarded for the thesis. __________________________, Graduate Coordinator ___________________ Susan Crawford, Ph.D. Date Department of Chemistry iv Abstract of SYNTHESIS AND CHARACTERIZATION OF CHIRAL OXOVANADYL (IV)- SALEN CATALYSTS AND VANADIUM-CATALYZED STEREOSELECTIVE EPOXIDATION REACTIONS by Diana Cheng Synthesizing pharmaceutical drugs with incorrect stereochemistry can lead to detrimental effects in one’s body. Therefore, developing a method that can yield high stereoselectivity is important in natural product and pharmaceutical drug syntheses. Epoxides are frequently used as intermediates in total synthesis of bioactive compounds due to their ability to create multiple chiral centers simultaneously, which can reduce the number of steps in a synthesis. The classic asymmetric epoxidations (Jacobsen’s and Sharpless-Vanadium epoxidation reactions) utilize metal catalysts to generate epoxides with high stereoselectivity. This research focuses on the development of optically active chiral oxovanadyl (IV) catalysts by utilizing salen ligands to offer an alternative methodology for catalytic epoxidation reactions. Vanadium catalysts are, in particular, of high interest due to their ability to effectively activate peroxides and transfer oxygen to alkenes. Eight unique oxovanadyl (IV) salen catalysts were synthesized and characterized by FT-IR and HR-ESI- v MS. The catalysts were employed in various epoxidation reactions with different substrates to test for epoxide formation and stereoselectivity. Epoxidizing a variety of non- functionalized alkenes gave yields between 20% - 52%, while functionalized alkenes (allylic alcohols) gave between 85% - 99% yield. Stereoselectivity was observed when epoxidizing aromatic alkenes and allylic alcohols using the catalysts synthesized. The results from this project suggest multiple plausible mechanisms, including a stepwise biradical pathway and Sharpless-type concerted pathway. _______________________, Committee Chair James Miranda, Ph.D. _______________________ Date vi ACKNOWLEDGEMENTS To my advisor, Dr. James Miranda, thank you for your patience with me through the program and your encouragement during the times when reactions didn’t work. I’m very fortunate to have joined your research group as an undergraduate student and even more fortunate to have continued my graduate research with you. Your positivity was very heart-warming and uplifting through the most difficult times in my research. To my committee members, Dr. Jacqueline Houston and Dr. Cynthia Kellen-Yuen, thank you for taking your time to read my thesis and giving me great feedback. I really appreciate the suggestions that you have given me to help polish my thesis. To my mentors, Dr. Claudia Lucero and Dr. Jeffrey Mack, thank you for all that you have done for me. If I ever needed help with anything, whether it be with teaching, research, or life advice, both of you were there for me, without hesitation at all. I cannot express to you how much this means to me. To Dr. Roy Dixon and Maria Santos, thank you for helping with the HR-ESI-MS instrument. This instrumentation was extraordinarily important for catalyst characterization. vii To my friends, Olga, Victor, and Morgan, thank you for being there for me. I am so grateful to have met you during my graduate program. We have become such great friends and shared so many memories and laughs. All I can say is we finally did it! To my family, I am forever grateful for your support and guidance through my life. I am so fortunate to have parents and siblings who are so understanding and patient. Thank you for all your unconditional love- it means so much to me. Words cannot express the gratitude I have for each of you and I could not have done it without you all viii TABLE OF CONTENTS Page Acknowledgements ........................................................................................................... vii List of Tables ................................................................................................................... xiii List of Figures .................................................................................................................. xiv List of Schemes .............................................................................................................. xviii List of Tables .................................................................................................................... xx List of Abbreviations ....................................................................................................... xxi Chapter 1. INTRODUCTION .......................................................................................................... 1 BACKGROUND ........................................................................................................... 8 1.1 Vanadium and Its Applications .................................................................... 8 1.2 Epoxidation Reactions ................................................................................. 9 1.2.1 Sharpless Vanadium-Epoxidation ...................................................... 9 1.2.2 Jacobsen’s Epoxidation .................................................................... 15 1.3 Nuclear Magnetic Resonance (NMR) Spectroscopy ................................. 26 1.3.1 Yield Determination .......................................................................... 26 1.3.2 Calculating Enantiomeric and Diastereomeric Excess ...................... 27 2. RESULTS AND DISCUSSION: OPTIMIZATION OF EPOXIDATION REACTIONS USING OXOVANADYL (IV) SALEN CATALYSTS ....................... 29 ix 2.1 Synthesis of Vanadyl (1R,2R)-N,N’-bis(3,5-di-tert-butylsalicylidenato)- 1,2-cyclohexane diamine catalyst. ............................................................ 30 2.2 Oxidant Study ............................................................................................ 32 2.3 Temperature Study ..................................................................................... 36 2.4 Solvent Study ............................................................................................. 38 2.5 Catalytic Loading Study ............................................................................. 39 2.6 Characterization of [1,2-bis(tert-butylperoxy)ethyl] benzene ................... 40 3. RESULTS AND DISCUSSION: EPOXIDATION REACTIONS AND STEREOSELECTIVITY ............................................................................................. 48 3.1 Sample synthesis of one chiral ligand: (1R,2R)-N,N’-bis(5-bromo- salicylidene)-1,2-cyclohexanediamine (Bromo ligand). ........................... 50 3.2 Epoxidation of Various Substrates using Synthesized Catalysts ............... 52 3.3 Mechanism ................................................................................................. 77 3.4 Other Reactions Tested .............................................................................. 91 4. CONCLUSIONS AND FUTURE WORK ................................................................... 93 5. EXPERIMENTAL ........................................................................................................ 95 A. Ligands ........................................................................................................ 96 B. Metal Complexes ...................................................................................... 102 C. Epoxidation Reactions ............................................................................... 109 x Appendix A. Characterization of ligands ........................................................................ 119 Spectra of (1R,2R)-N,N’-bis(3-methyl-salicylidene)-1,2- cyclohexanediamine ....................................................................................... 120 Spectra of (1R,2R)-N,N’-bis(methoxy-salicylidene)-1,2- cyclohexanediamine ....................................................................................... 122 Spectra of (1R,2R)-N,N’-bis(5-bromo-salicylidene)-1,2- cyclohexanediamine ....................................................................................... 124 Spectra of 1,1’[(1R,2R)-1,-cyclohexanediylbis[(E)- nitrilomethyllidyne]]bis-2-naphthalenol ........................................................ 126 Spectra of (1R,2R)-N,N’-bis(nitro-salicylidene)-1,2-cyclohexanediamine .... 128 Spectra of (1R,2R)-N,N’-bis(3,5-dibromo-salicylidene)-1,2- cyclohexanediamine ......................................................................................
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