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ENANTIOSELECTIVE ADDITIONS of ALLYL INDIUM REAGENTS to ALDEHYDES a Thesis Presented to the Faculty of the Department of Chemistr

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ENANTIOSELECTIVE ADDITIONS of ALLYL INDIUM REAGENTS to ALDEHYDES a Thesis Presented to the Faculty of the Department of Chemistr ENANTIOSELECTIVE ADDITIONS OF ALLYL INDIUM REAGENTS TO ALDEHYDES 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 Addison James Beckemeyer SPRING 2018 © 2018 Addison James Beckemeyer ALL RIGHTS RESERVED ii ENANTIOSELECTIVE ADDITIONS OF ALLYL INDIUM REGENTS TO ALDEHYDES A Thesis by Addison James Beckemeyer Approved by: __________________________________, Committee Chair Dr. Claudia Lucero __________________________________, Second Reader Dr. Cynthia Kellen-Yuen __________________________________, Third Reader Dr. Mary McCarthy-Hintz ____________________________ Date iii Student: Addison James Beckemeyer 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 ___________________ Dr. Susan Crawford Date Department of Chemistry iv Abstract of ENANTIOSELECTIVE ADDITIONS OF ALLYL INDIUM REGENTS TO ALDEHYDES by Addison James Beckemeyer The enantioselective allylation of aldehydes are considered one of the most useful carbon-carbon bond forming reactions in synthetic chemistry. This reaction type is of such use because it allows access to a wide range of homoallylic alcohols, which are considered a common building block for a number of biologically active natural products. Although there are a number of asymmetric allylation strategies reported currently, most processes involve: reagents or catalysts sensitive to air and moisture, catalysts incorporating toxic metals, toxic allylstannanes, and/or stochiometric amounts of chiral initiators. The use of chiral imidazolidinones as catalysts to perform directed additions of allyl indiums to aldehydes was investigated. This approach would eliminate many of the disadvantageous means or materials used in other methodologies while providing the same chiral alcohols. A range of aldehydes and allyl halides were studied using this methodology. Products were recovered in high yield (64-93%). One reaction proved asymmetric with an enantiomeric excess (ee) of >99%. Changes to solvent, catalyst, and co-catalyst were investigated illuminating key insights into the way in which this reaction proceeds. v Results of these assorted studies revealed information about catalyst function and the rate of reactions possible in this one-pot mixture. _______________________, Committee Chair Dr. Claudia Lucero _______________________ Date vi ACKNOWLEDGEMENTS I would like to acknowledge Dr. Lucero for being such an open, accessible, and understanding mentor. Thank you for always being supportive and making time through such a stress-inducing process. Your practicality and expertise are what brought me to finish this endeavor. I would like to thank Dr. Kellen-Yuen and Dr. McCarthy-Hintz for being on my thesis committee. The amount of time you were both willing to input into my thesis is invaluable to me. Thank you to my lab research group. Especially Daniel Ferreyra Orozco who was always willing to chat about our research or climb some rocks. Thank you to my parents and loving girlfriend for supporting me through my decision to pursue a master’s degree. I would not be the complete person I am today without all three of you. Finally, I would like to acknowledge the whole CSUS chemistry department for making me feel truly welcome at a new school. I’ve never felt as included in my life as I have felt here. Specifically, Dr. Linda Roberts for giving me an initial chance and believing in me. vii TABLE OF CONTENTS Page Acknowledgements ................................................................................................ vii List of Tables .......................................................................................................... xi List of Figures ........................................................................................................ xii List of Schemes ..................................................................................................... xiii Chapter 1. INTRODUCTION …………………………………………………………..….. 1 1.1 Overview ................................................................................................ 1 1.2 Nucleophilic Additions ........................................................................... 3 1.3 Indium-mediated Chemistry .................................................................... 5 1.4 Enantioselective Additions to Carbonyls ............................................... 10 1.5 MacMillan’s Imidazolidinone Organocatalysts™ .................................. 12 1.6 Methodology and Analytical Methods ................................................... 17 2. RESULTS AND DISCUSSION ....................................................................... 22 2.1 Overall Results...................................................................................... 22 2.1.1 Mosher Ester Analysis ............................................................ 23 2.2 Addition of Various Allyl Halides to trans-Cinnamaldehyde ................. 34 2.2.1 Crotylation of trans-Cinnamaldehyde ..................................... 36 2.3 Optimizing the Allylation of Hydrocinnamaldehyde.............................. 40 2.4 Benzaldehyde Functional Group Study ................................................. 42 viii 2.4.1 Methoxy Functional Group ..................................................... 43 2.4.2 Nitro Functional Group ........................................................... 47 2.5 Lack of Enantioselectivity ..................................................................... 49 2.6 Attempts to Induce Enantioselectivity ................................................... 51 3. CONCLUSIONS AND FUTURE WORK ........................................................ 55 4. EXPERIMENTAL ........................................................................................... 58 4.1 Spectra and Chromatograms .................................................................. 58 4.2 Product Synthesis and Characterization ................................................. 58 4.2.1 (E)-1-phenylhexa-1,5-dien-3-ol (12) ....................................... 58 4.2.2 (E)-5-methyl-1-phenylhexa-1,5-dien-3-ol (13) ........................ 60 4.2.3 (E)-4-methyl-1-phenyl-3,4-hexa-1,5-dien-3-ol (14) ................ 61 4.2.4 1-phenylhex-5-en-3-ol (15) ..................................................... 63 4.2.5 (S)-1-(2-methoxyphenyl)but-3-en-1-ol (16) ............................ 64 4.2.6 1-(2-fluorophenyl)but-3-en-1-ol (17) ...................................... 66 4.3 General Procedure for Mosher Ester Derivatization ............................... 67 4.4 General Procedure for Catalyst Study .................................................... 68 4.4.1 Reactions Involving trans-Cinnamaldehyde ............................ 68 4.4.2 Reactions Involving 2-Methoxybenzaldehyde ......................... 69 Appendix A. Spectral Data of (E)-1-phenylhexa-1,5-dien-3-ol (12) ...................... 71 Appendix B. Spectral Data of (E)-5-methyl-1-phenylhexa-1,5-dien-3-ol (13) ....... 77 ix Appendix C. Spectral Data of (E)-4-methyl-1-phenyl-3,4-hexa-1,5- dien-3-ol (14) ......................................................................................................... 84 Appendix D. Spectral Data of 1-phenylhex-5-en-3-ol (15) .................................... 89 Appendix E. Spectral Data of (S)-1-(2-methoxyphenyl)but-3-en-1-ol (16) ............ 96 Appendix F. Spectral Data of 1-(2-fluorophenyl)but-3-en-1-ol (17) .................... 103 References ............................................................................................................ 110 x LIST OF TABLES Tables Page 1. Summary of Successfully Synthesized Alcohols.…………………………….. 22 2. Results for Allylation Technique Applied to Various Aldehydes and Allyl Halides................................................................................................................34 3. Optimization trials for the Allylation of Hydrocinnamaldehyde…….………...41 4. Results of Benzaldehyde Functional Group Study……….………...………….43 5. Results for Other Catalytic Trials in an Attempt to Induce Enantioselectivity……………………………………………………………...52 xi LIST OF FIGURES Figures Page 1. Representative Biologically Active Natural Products ......... .…………………. 2 2. Proposed Allylindium Intermediate Species and Their Oxidation States…..…. 8 3. L-Proline Compared to Chiral Imidazolidinone Catalysts……….………...…. 13 1 4. H NMR of (E)-1-phenylhexa-1,5-dien-3-ol (12) in CDCl3……………….…. 25 5. 1H NMR of Non-Purified (E)-1-phenylhexa-1,5-dien-3-ol R-Mosher Ester in CDCl3………………………………………………………………………. 27 6. 1H-1H COSY of Non-Purified (E)-1-phenylhexa-1,5-dien-3-ol R-Mosher Ester in CDCl3...………….………………….………………….…. 29 1 7. H NMR of (S)-1-(2-methoxyphenyl)but-3-en-1-ol (16) in CDCl3…………... 31 8. 1H NMR of Non-Purified (S)-1-(2-methoxyphenyl)but-3-en-1-ol R-Mosher Ester in CDCl3……………..………………….……………..…….. 32 9. 1H-1H COSY of Non-Purified (S)-1-(2-methoxyphenyl)but-3-en-1-ol R-Mosher Ester in CDCl3………………………….……………………….…. 33 10. 1H NMR of Crotylation Product of trans-Cinnamaldehyde (14)………...……. 37 11. Relative Calculated Energies of Iminium Ion Intermediate Formed Between Catalyst 7 and 2-Methoxybenzaldehyde……………..……………….……….. 45 xii LIST OF SCHEMES Scheme Page 1. Indium-mediated addition
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