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Difluoroboronate Urea-Induced Acid Amplification for Insertion Chemistry

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Difluoroboronate Urea-Induced Acid Amplification for Insertion Chemistry Difluoroboronate Urea-Induced Acid Amplification for Insertion Chemistry A Thesis Presented in Partial Fulfillment of the Requirements for the degree of Master of Science in the Graduate School of The Ohio State University By Erica Dawn Couch, B. S. Graduate Program in Chemistry The Ohio State University 2014 Committee: Professor Anita E. Mattson (Advisor) Professor Claudia Turro Copyright by Erica Dawn Couch 2014 Abstract Development of a new enhanced boronate urea that benefits from internal coordination of the urea carbonyl to a strategically placed Lewis acid has enabled a new direction in hydrogen bond donor (HBD) catalysis. Activation of α-nitrodiazocarbonyl compounds has elicited carbene- like reactivity, allowing for access to metal-free insertion reactions. Recent developments have utilized the difluroboronate urea with an organic acid cocatalytically to promote insertion reaction with aryldiazoacetates. These reactions are proposed to occur through a HBD induced heteroatom acidity amplification, facilitating protonation of the α-aryldiazoacetates, which can undergo a nucleophilic attack by the conjugate base. Understanding of the insertion mechanism has led to asymmetric cocatalytic variations of the insertion reactions utilizing both chiral acids with achiral HBD catalyst and chiral HBD catalyst with an achiral acid. Work towards an asymmetric reaction has illuminated the one lacking feature of the boronate catalyst: its ability to achieve enantioselectivity, which has been an ongoing problem to advancements with these catalysts. Herein, development of a new chiral catalyst design and a new metal-free approach to a selective insertion reaction are discussed. ! ii! ! Dedication I would like to dedicate this work to my family. “Although we may not have it all together, together we have it all.” ! iii! ! Acknowledgements I would first like to thank my advisor, Anita Mattson, for affording me the opportunity to work in her lab. Her guidance and support has allowed me to accomplish more than I would have ever expected to in my short time here at The Ohio State University. I would also like to thank all of the other faculty and staff here at The Ohio State University, especially Professors Claudia Turro for her help and guidance towards accomplishing my degree and James Stambuli for always being available to help and to humor. I would like to thank my undergraduate advisor, LuAnne McNulty, for her constant advice in what to do next, whether it is in chemistry or in life, as well as my undergraduate department chair, Stacey O’Reilly, for her positivity that she was able to instill in me and several others throughout our undergraduate careers. I would also like to thank my high school chemistry teacher and softball coach, Dick “Doc” Hines, for never holding me back from being me, whether it was in a classroom or on the field. Throughout my time at Ohio State, I have met several people who mean more to me than they will ever know. I first and foremost have to thank Tyler Auvil for all of his patience and guidance in training me and working with me on pretty much every project I ever touched during my time here. You have made me the chemist and person that I am today, and I don’t think that I will ever be able to repay for making my time here worth it. I would also like to thank Sonia So for being the best friend I could have asked for in grad school. I don’t know what I would have done in lab without our laughs, talks, and awkward run-ins! I am so happy that the majority of ! iv! ! my time overlapped with yours so that we were able to spend as much time together as we did, in the least creepy way possible. Josh Wieting for his entertainment in the lab, and his and his wife’s friendship outside of lab, “eat the brat, eat the brat!” Chi “Chip” Li for being an inspiration to work harder no matter what is going on around you, I didn’t expect for our friendship to grow as much as it did but I am happy to know that I will always have you to call. Veronica for always being willing to run, and my first summer here, I will never forget it! Mike “Moke” Visco just for always being here, you seriously are my new little brother and it’s goingt to be weird to walk around a room without having to walk around you. As well as several other really good friends I have met at my time here including: Luke “Lil Moke” McCroskey, Andrew “Angrew” Schafer, Dr. Tom Fisher, Kelsey Miles, the Forsyth group lunch boys, Joe “Bro” Castle, Greg Abernathy, Daniel Miller and several others. Lastly, I would like to thank my family and friends for all of their love and support. My best friend, Danielle Wright, for being a friend at anytime of the day and night even if it took me months to call! My grandparents, especially my grandmas “mamaw” and “mammie” for always pushing me to be a better woman and for living as an example of what it meant to be better woman. I would like to thank my brothers for being them and being there they don’t know what they mean to me. My sister, Kristen, who even when I wished she was dead, I was praying that nothing would ever happen to her. I love you and I am happy we have become as good of friends as we have. Most importantly, however, I have to thank my parents. My dad for never hesitating to be there when I called and for always keeping me as his little girl, and my mom for not only being my biggest fan, but for being the bestest friend I will ever have. ! v! ! Vita May 2008…………………………………………………………………... Anderson High School May 2012………………………………………………………. B.S. Chemistry, Butler University 2012 to present……………………….… Graduate Research Assistant, The Ohio State University Publications Couch, E. D.; Auvil, T. J.; Mattson, A. E. “Urea-Induced Acid Amplification: A New Approach for Metal-Free Insertion Chemistry” Chem. Eur. J. 2014, 20, 8283 – 8287. Field of study: Chemistry ! vi! ! Table of Contents Abstract ............................................................................................................................................ ii Dedication ....................................................................................................................................... iii Acknowledgements ......................................................................................................................... iv Vita .................................................................................................................................................. vi List of Tables .................................................................................................................................... x List of Figures ................................................................................................................................. xi List of Schemes .............................................................................................................................. xii Chapter 1: Chiral Hydrogen Bond Donor Design and Development .............................................. 1 1.1 (Thio)urea Hydrogen Bond Donor Catalysts History ................................................................ 2 1.1.1 Molecular Recognition ..................................................................................................... 2 1.1.2 History of Dual HBD Catalysis ........................................................................................ 4 1.1.3 Chiral (thio)urea catalysis ................................................................................................. 7 1.2 Design Strategies for Enhance Dual HBD Catalysts ............................................................... 12 1.2.1 3,5-bis(trifluoromethylphenyl) Moiety in HBD Catalysis ............................................. 12 1.2.2 Chiral Acidifying Groups ............................................................................................... 14 1.2.3 Internal Brønsted Acid Assistance ................................................................................. 17 1.2.4 Preorganizing and Acidifying Linkers ........................................................................... 19 1.3 Internal Lewis Acid-Assisted Dual HBD Catalysis: Boronate Ureas ...................................... 22 1.3.1 Catalytic Design Background ......................................................................................... 22 ! vii! ! 1.3.2 Catalytic Reactivity ........................................................................................................ 25 1.3.3 Catalyst Acidity .............................................................................................................. 33 1.4 Design Strategies for Enhance Internal Lewis Acid-Assisted Dual HBD Catalysis: Boronate Ureas .............................................................................................................................................. 36 1.4.1 Strategies ........................................................................................................................ 36 1.4.2 Synthesis ......................................................................................................................... 38 1.4.3 New Avenues .................................................................................................................. 40 1.5 Experimental Section ............................................................................................................... 42 1.5.1 Preparation of Model Catalyst .......................................................................................
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