STRESS RELIEF: EXERCISING LEWIS ACID CATALYSIS FOR DONOR-ACCEPTOR CYCLOPROPANE RING-OPENING ANNULATIONS, A BASIS FOR NEW REACTION METHODOLOGIES A Dissertation Presented to The Academic Faculty by Marchello Alfonzo Cavitt In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the School of Chemistry and Biochemistry Georgia Institute of Technology December 2015 Copyright© 2015 by Marchello Cavitt STRESS RELIEF: EXERCISING LEWIS ACID CATALYSIS FOR DONOR-ACCEPTOR CYCLOPROPANE RING-OPENING ANNULATIONS, A BASIS FOR NEW REACTION METHODOLOGIES Approved by: Dr. Stefan France, Advisor Dr. Christoph Fahrni School of Chemistry and Biochemistry School of Chemistry and Biochemistry Georgia Institute of Technology Georgia Institute of Technology Dr. Charles Liotta Dr. Christopher Jones School of Chemistry and Biochemistry School of Chemical Engineering Georgia Institute of Technology Georgia Institute of Technology Dr. Gary Schuster Dr. Leslie Gelbaum School of Chemistry and Biochemistry School of Chemistry and Biochemistry Georgia Institute of Technology Georgia Institute of Technology Date Approved: November 5, 2015 This dissertation is dedicated in loving memory to my great grandmother, Thelma Cavitt, grandmother, Mary Cavitt, and great aunt, Marie McPherson, who reared me in the absence of my parents. Despite their hardships and economic challenges, they endured and remained diligent in instilling the importance of education, perseverance, and integrity in me. For their love, support, and sacrifices made on behalf of my sisters and me, I will forever be grateful. To add to that illustrious cadre of women in this dedication, I offer my sincere gratitude to my best friends, whom I have known for ten years---Daniel Jackson, M.D. and Corey Roberson. D.D.S. Without these intelligent, funny, and supportive men to keep me motivated and driven, I would have been deterred from achieving such a feat and not adhered to my fraternal motto: “achievement in every field of human endeavor” according to the abiding principles and stalwart values of Kappa Alpha Psi Fraternity, Inc. While they are not my relatives or fraternal kin, I am privileged to honor them as my brothers with this auspicious dedication. ACKNOWLEDGEMENTS First and foremost, I would like to give my greatest appreciation and admiration to my advisor, Professor Stefan France, for permitting me to study and perform research in his group. Dr. France allowed me to pursue my intellectual curiosity in fields such as science policy [Sam Nunn Security Fellow], medicinal chemistry [AbbVie], methodology development, and natural product synthesis. Because of this academic freedom, I obtained private industrial experience and expanded my scholarly skills with regard to critical thinking, problem solving, communication, cognitive, and competence skills as they relate to chemistry and broader issues at the nexus of science and policy. Moreover, I want to thank Professor France for his mentorship, guidance, and support for my professional endeavors. For this, I will always be grateful. In addition to my advisor, I am appreciative of my committee members. I would like to give thanks to the professors who have served as role models and provided advice: Dr. Christoph Fahrni, for his guidance toward the completion of my studies; Dr. Gary Schuster, for his encouragement and professional advice on my career objectives; Dr. Charles Liotta, for being a great teacher and directing me to reshape my thinking in the light of “positivity;” Dr. Christopher Jones, for writing recommendation letters and discussing my academic goals at Georgia Tech; Dr. Leslie Gelbaum for training and teaching me the principles NMR spectroscopy, being a great consultant in answering and interpreting complex NMR spectra, having high expectations of me, and for consistently encouraging me and providing me with proactive approaches to overcome hardship in my academic pursuits; and Dr. Raquel Lieberman, for allowing me to iv participate in her biochemical collaboration. While the faculty mentioned are influential, my colleagues had a profound effect on my progression as well. When I became part of the France group at Georgia Tech, I received two outstanding graduate mentors, Drs. Dadasaheb Patil and Lien Phun. I am extraordinarily indebted to Dr. Patil for training me in laboratory techniques and allowing me to participate in and contribute to the various projects included in this thesis. Without his support and motivation, I would not have been as inspired to investigate and explore complex scientific questions. Also, I appreciate Dr. Lien Phun for her laboratory training and inclusion on the heteroaromatic homo-Nazarov research. Both of these individuals are representative examples of the definitions: driven, hard-working, determined, smart, and kind colleagues. In this cadre of friends, I also include Dr. Deepti Sharma for being a great support through my early graduate experience, and Dr. Rebecca Key, a fellow colleague, who I have grown quite fond of through our late nights and long discussions in completing our dissertation studies. She is a great friend. I am extremely grateful to and appreciative of all these individuals. I will cherish our journeys together and look forward to our professional relationships and growing friendships in the future. Throughout my research endeavors, I have had other amazing friends and colleagues. I would like to acknowledge Dr. Kaysia Ludford and Aireen Romu who were great study partners, confidants, and my support system at the University of Michigan. Furthermore, I give my deepest gratitude to Dr. Ariel Marshall for consistently being an outstanding best friend throughout my time at Georgia Tech. I am grateful for the many late night pep talks, prayers, and discussions. Most of all, I will miss the humor we shared and dance-offs to music in the office and lab areas. I cannot forget my dear friend of ten v years, Katherine Foston. She was instrumental in my motivation, perseverance, and determination throughout my graduate studies. Also, I would like to thank Drs. Damien Young and Brandon Quillian for their professional advice with regard to my future endeavors and for being role models in their respective chemical fields. From my undergraduate to graduate studies, I was influenced by many educators and mentors, in particular, Dr. Mordean Taylor-Archer, Diane Whitlock, Sharonda Holmes, Ed Laster, and Dr. Keith Oden. I would like to give my deepest gratitude to these individuals who believed in me and always reminded me of my potential, especially, Dr. Keith Oden, who encouraged and motivated me on numerous occasions in my doctoral studies. His guidance, support, and positive attitude have been invaluable. In my opinion, he has an immeasurably profound impact on graduate students at Georgia Tech, and I am fortunate to have encountered this great mentor, friend, and educator along my doctoral pursuit. Overall, without all these great men and women, I would not have learned nor had the opportunities to grow in the values of leadership and scholarship. Besides my undergraduate and graduate instructors, some high school educators at Owensboro High School and Frank Cody High School had an impact on my life as well. I would like to thank Lori Thurman, a high school social studies teacher and advisor, for cultivating my leadership potential early and nurturing my eager ambition. As a result of the exposure she afforded me through the Kentucky Youth Assembly and student government, I was able to appreciate the importance of public service, academics, and achievement. Furthermore, Lori demonstrated a devout and sincere compassion for my sisters and me when a difficult family situation arose. Both Lori and Anita Burnette, my former high school principal, were caring and kind with open arms to offer their assistance vi during an unfortunate family emergency; for this, I will always be thankful. At Frank Cody High School, I encountered other amazing educators such as Ms. Beverly Rohde, Mrs. Sharon Walker, Mrs. Kelly Booker, and Ms. Mary Barnes. All of these women were outstanding influences during my senior year at Frank Cody High School. Without their commitment to my sustained success, I would have traveled down a path antithetical to progress and achievement. All things considered, I would be remiss if I did not acknowledge the institutions and organizations which invested in me and my future. Throughout my academic progress, I have been very fortunate to attend outstanding institutions of higher learning and receive financial support from universities and various private and public foundations. I would like to thank the University of Louisville for providing me with the Woodford R. Porter Scholarship and the Minority Teacher Recruitment Project Scholarship. I am grateful for the Rackham Merit Fellowship from the University of Michigan. I would like to thank the Alfred P. Sloan Foundation for the NACME Alfred P. Sloan Fellowship, the Ford Foundation for the Ford Diversity Fellowship, and the National Science Foundation for the National Science Foundation Graduate Research Fellowship. I would like to thank the Georgia Institute of Technology for the Presidential Fellowship and the John D. and Catherine T. MacArthur Foundation for the Sam Nunn Security Fellowship. I credit all of these universities and foundations with my academic growth and development, and I am proud to be an alumnus. Finally, I am especially grateful to the American taxpayer and my country, the United States