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Boron-Based Lewis Acids: Towards Intramolecular Frustrated Lewis Pairs and Enantioselective Catalysis

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Boron-Based Lewis Acids: Towards Intramolecular Frustrated Lewis Pairs and Enantioselective Catalysis Boron-Based Lewis Acids: Towards Intramolecular Frustrated Lewis Pairs and Enantioselective Catalysis by Jolie Zi Ning Lam A thesis submitted in conformity with the requirements for the degree of Doctor of Philosophy Department of Chemistry University of Toronto © Copyright by Jolie Zi Ning Lam 2020 Boron-Based Lewis Acids: Towards Intramolecular Frustrated Lewis Pairs and Enantioselective Catalysis Jolie Zi Ning Lam Doctor of Philosophy Department of Chemistry University of Toronto 2020 Abstract A rapid development of metal-free, main group compounds for small molecule activation and as hydrogenation catalysts was triggered after the disclosure of H2 activation by sterically hindered Lewis acids and bases over a decade ago. The combination of a Lewis acid and base with unquenched reactivity was later coined as a “frustrated Lewis pair” (FLP). In this research, boron-based Lewis acids were studied for their application as catalysts in FLP chemistry, with an emphasis on exploring the production of chiral FLPs and intramolecular FLPs. In the exploration towards enantioselective catalysis, 3,5-bicyclic aryl piperidines were synthetically modified to produce B/N FLPs and were shown to activate dihydrogen, demonstrating the potential for expanding chiral FLP templates beyond the typical chiral ligands used in transition metal complexes. Chiral borenium cations were generated from different families of carbene-borane adducts, in which their chirality resides on either the carbene or the borane. Catalytic studies found that they were able to effect imine reduction without epimerisation of the resulting chiral amine, and the reactivity and enantioselectivity of these cations were found to be inversely proportional to steric demands. In the exploration towards a cationic intramolecular FLP, a borenium cation with a pendant phosphine was synthesized through hydroboration of a phosphinoalkene with an isolable B-H borenium cation, and its FLP reactivity was investigated. ii Finally, initial efforts towards the production of a bisborane-carbene as a tri-functionalized FLP were documented. iii Dedicated in loving memory of my grandmother, Cheung Shou Wah iv Acknowledgments I was fortunate to meet many people along the way that made this 5-year journey fruitful beyond expectation. First and foremost, I would like to thank my supervisor Professor Doug Stephan for the privilege of working in his research group, for always having an open door for chemistry and career discussions, and your support in our endeavors outside of research. Your guidance and advice had been very helpful, both in my research and my professional development. Thank you also for willing to let your students freely explore their scientific interest. Not only was I able to work on what I find interesting, I was also able to simultaneously learn from others about chemistry far beyond the scope of this thesis. I must also extend my thanks to my committee members, Professor Robert Morris and Professor Mark Taylor, for your helpful suggestions and feedback in this research through committee meetings and seminars. I would like to thank all the past and present Stephan group members for their patience, guidance and support. I have been fortunate to work with and learn from many talented chemists over the last five years from all over the world. Thank you for all the valuable discussions and your patience in passing on your knowledge. All of you has helped me grown so much as a researcher. Thank you also for the friendship, for all the fun times we’ve had outside of work, and for sharing your stories. You have taught me more than just chemistry. I must also extend my gratitude to Shanna Pritchard, who has kept us in check and helped this research group run smoothly. Special thanks must also be given to those that helped with the editing of this thesis: Ryan Andrews, Karlee Bamford, Levy Cao, Louie Fan, Felix Krischer, James LaFortune, Chris Major, Alex Waked, and Diya Zhu. Thank you to my collaborators, Benjamin Günther, Dr. Jeffrey Farrell, Dr. Patrick Eisenberger, Brian Bestvater, Dr. Susanna Sampaolesi, Dr. Paul Newman, Dr. Jotham Coe, Professor Rebecca Melen, and Professor Cathleen Crudden, for the amazing work and insightful discussions. It has been a pleasure working with you and learning from you. I must also give my thanks to Rose Balazs from Analest, Chung Woo Fung from AIMS, and the wonderful past and present NMR staff, Dr. Darcy Burns, Dr Jack Sheng, Dr. Sergiy Nokhrin, Dmitry Pichugin, and Dr. Karl Demmans for analytical help beyond the call of duty. A special shout out to my friends that I consider my brothers and sisters, both in Canada and in Hong Kong for their support. Thank you for believing in me and cheering me on when I needed v it. Thank you to Mom and Dad, for your unconditional love and support. Thank you for putting your complete trust in my career choices and allowing me to pursue my goals without worries and hesitation. Last and certainly not least, thank you to Louie Fan, for being my personal prescription of antidepressant. Words cannot describe my gratitude for everything you’ve gone through to make me smile. Thank you all for making a mark in this chapter of my life. You have made it a lot easier to write it. vi Table of Contents Acknowledgments ...................................................................................................................... v Table of Contents ..................................................................................................................... vii List of Figures ........................................................................................................................... xi List of Schemes ....................................................................................................................... xiv List of Tables ........................................................................................................................ xviii List of Symbols and Abbreviations .......................................................................................... xix Chapter 1 Introduction ........................................................................................................... 1 1.1 Science and Humankind.................................................................................................. 1 1.2 Catalysis ......................................................................................................................... 2 1.2.1 Background ......................................................................................................... 2 1.2.2 Properties, Sources and Uses of Boron ................................................................ 3 1.2.3 Boron Chemistry ................................................................................................. 4 1.3 Frustrated Lewis Pairs..................................................................................................... 6 1.3.1 History ................................................................................................................ 6 1.3.2 Mechanistic Investigation and FLP Reactivity ..................................................... 8 1.3.3 FLP Hydrogenation Catalysis .............................................................................10 1.4 Scope of Thesis ..............................................................................................................11 1.5 References .....................................................................................................................14 Chapter 2 Synthesis and Reactivity of B/N FLPs Derived from 3,5-Bicyclic Aryl Piperidines ............................................................................................................................22 2.1 Introduction ...................................................................................................................22 2.1.1 Importance of Chirality ......................................................................................22 2.1.2 Transition Metal-Catalyzed Asymmetric Hydrogenation ....................................24 2.1.3 FLP-Catalyzed Asymmetric Hydrogenation .......................................................25 2.2 Results and Discussion ..................................................................................................28 vii 2.2.1 Synthesis of 3,5-Bicyclic Aryl Piperidines..........................................................28 2.2.2 Hydroboration of the Styrene Derivative ............................................................30 2.2.3 Lewis Acidity Determination..............................................................................35 2.2.4 FLP Reactivity ...................................................................................................38 2.3 Conclusion .....................................................................................................................40 2.4 Experimental Section .....................................................................................................40 2.4.1 General Considerations ......................................................................................40 2.4.2 Synthesis of Compounds ....................................................................................42 2.4.3 Procedures of Gaseous Experiments ...................................................................48 2.4.4 Computational Details ........................................................................................49
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