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Diastereoselective Transformations of Macrocyclic 1,4-Diketones for the Synthesis of Cy- Clobutane-Containing Natural Products

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Diastereoselective Transformations of Macrocyclic 1,4-Diketones for the Synthesis of Cy- Clobutane-Containing Natural Products Diastereoselective Transformations of Macrocyclic 1,4-Diketones for the Synthesis of Cy- clobutane-containing Natural Products by Kara F. Johnson A dissertation submitted to the Graduate Faculty of Auburn University in partial fulfillment of the requirements for the Degree of Doctor of Philosophy Auburn, Alabama December 12, 2020 Keywords: Diastereoselective, macrocyclic diketone, cyclobutane, transannular McMurry, Grignard addition Copyright 2020 by Kara F. Johnson Approved by Bradley L. Merner, Chair, Associate Professor of Chemistry and Biochemistry Doug Goodwin, Professor and Chair of Chemistry and Biochemistry Ming Chen, Assistant Professor of Chemistry and Biochemistry Rashad Karimov, Assistant Professor of Chemistry and Biochemistry Abstract CHAPTER 1 Macrocyclic conformation has been investigated since the 1950s. The understanding of this phenomenon has been applied to predict and explain diastereoselective reactions to macro- cyclic systems since this time, and correlation is observed between the low-energy conformation of a macrocycle and the diastereoselectivity of reactions to that system. High levels of diastere- oselectivity have been observed for Grignard reactions of macrocyclic 1,4-diketones. In all of the macrocycles investigated, ring size proved to be the greatest contributor to diastereoselectivity. As the size of the macrocyclic 1,4-diketone system employed decreases, the observed diastere- oselectivity of the 1,2-addition increases. For vinyl Grignard additions other factors affecting the observed diastereoselectivity include Grignard halide, solvent, and bridging motif. CHAPTER 2 Based on the results obtained from the studies of the Grignard reaction to macrocyclic 1,4-diketones, an investigation of enolate alkylations to these same macrocyclic diketones as a means to alkylate the α and α' positions diastereoselectively was undertaken. High levels of dia- stereoselectivity where obtained in these vicinal alkylation reactions, and the resulting macrocy- clic 1,4-diketones were subsequently subjected to a five step sequence, featuring a transannular McMurry reaction, to afford di-O-methylendiandrin A as well as other lignan-type cyclobutane- containing compounds. 2 Acknowledgments I would like to acknowledge those who have both pushed and supported me in my jour- ney to this point. Firstly, I would like to express my gratitude to Prof. Bradley L. Merner for provid- ing me the opportunity to learn under his guidance. He has taught me more than I could have imagined and has pushed me to grow as a scientist beyond the bounds of which I felt capable. I will carry these lessons with me into future endeavors as I continue to learn and grow throughout my life. I also wish to thank my committee members: Prof. Doug Goodwin, Prof. Rashad Karimov, Prof. Ming Chen, and Prof. Angela Calderón for their time, support, and suggestions. I also would like to thank the Auburn University department of Chemistry and Biochemis- try for the opportunity to learn from so many incredible professors and mentors both in classes and as a teaching assistant. My gratitude especially goes to Dr. Michael Meadows and Dr. Alvaro Herrera for teaching me so much about NMR spectroscopy and instrumentation. I have gained valuable knowledge and experience from both of these men as I served under them in the NMR facility. Also, a special thanks to Dr. Melissa Boersma for her help and instruction in mass spec- trometry. My deepest gratitude also belongs to my lab mates throughout my time in the Merner group. Nirmal, Ana, Caroline, Nirob, Sydney, Hank, Meng, and Jacob have all been a source of encouragement and have pushed me to grow as a leader and scientist. Other friends within the department, especially Jessica Krewall, Julie Niklas, and Ethan Hiti, have made my time here so much better, and I am so grateful for your friendship. Lastly, I need to thank my church families at Auburn and Rose Hill for praying with me and for me and serving as constant support to keep going; my parents and siblings who have been both spiritually and physically present to support me; Rylie and Calum who have blessed my life beyond understanding with joy and perspective; and my loving husband, Scott, who has stood beside me, pushed me forward, and held me up every step of the way. God gave me these people to help strengthen me for this journey. It is only through His strength that I am here, and I could not be more grateful for His provision, salvation, and strength. 3 Table of Contents Abstract ..................................................................................................................................................... 2 Acknowledgments ..................................................................................................................................... 3 List of Tables ............................................................................................................................................. 6 List of Figures ............................................................................................................................................ 7 List of Schemes ......................................................................................................................................... 9 List of Abbreviations ................................................................................................................................ 11 Chapter 1 Stereoselective Reactions of Macrocycles ............................................................................. 15 1. Introduction ............................................................................................................................. 15 1.1 Conformations of Macrocycles ............................................................................................. 15 1.1.1 General Observations ........................................................................................................ 15 1.1.2 Conformations of Medium-Sized Ring Systems ................................................................ 16 1.1.3 Conformation of Large Ring Systems ............................................................................... 19 1.2 Early Examples of Stereoselective Reactions of Macrocycles ............................................. 25 1.2.1 Kinetic Enolate Alkylations ................................................................................................ 26 1.2.2 Conjugate Additions .......................................................................................................... 28 1.2.3 Reductions ......................................................................................................................... 30 1.2.4 Epoxidations ...................................................................................................................... 31 1.2.5 Syn-dihydroxylations with OsO4 ........................................................................................ 36 1.2.6 Other Conformationally Controlled Transformations ......................................................... 37 1.3 More Recent Examples of Stereoselective Reactions of Macrocycles ................................ 38 1.4 Diastereoselective Grignard Reactions of Macrocyclic 1,4-Diketones ................................. 41 1.5 Future Directions .................................................................................................................. 49 1.6 Conclusions .......................................................................................................................... 50 References .............................................................................................................................................. 52 Chapter 2 Regioselective Formation of 1,2,3,4-Tetrasubstituted Cyclobutanes ..................................... 55 2. Introductions ........................................................................................................................... 55 4 2.1 [2+2] Photocycloaddition Reactions for Assembling 1,2,3,4-Tetrasubstituted Cyclobutane Ring .................................................................................................................................... 55 2.1.1 [2+2] Photocycloaddition Reactions with No Added Catalysts .......................................... 57 2.1.2 Templated [2+2] Photocycloaddition Reactions ................................................................ 62 2.1.3 Metal-catalyzed [2+2] Photocycloaddition Reactions ........................................................ 66 2.1.4 Organo-catalyzed [2+2] Photocycloaddition Reactions ..................................................... 68 2.1.5 Limitations to the [2+2] Photocycloaddition ....................................................................... 69 2.2 Other Methods for Assembling a 1,2,3,4-tetrasubstituted Cyclobutane ............................... 70 2.2.1 [4π]photocyclizations ......................................................................................................... 70 2.2.2 Intramolecular Direct Ring Closure .................................................................................... 71 2.2.3 Rearrangements ................................................................................................................ 74 2.2.4 Transannular McMurry of Macrocyclic 1,4-Diketones for the Assembly of 1,2,3,4- tetrasubstituted Cyclobutanes ................................................................................................................
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