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Ring-Opening Reactions of Cyclopropanated Heterobicyclic Alkenes

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Ring-Opening Reactions of Cyclopropanated Heterobicyclic Alkenes Ring-opening Reactions of Cyclopropanated Heterobicyclic Alkenes by Emily Terada Carlson A Thesis presented to The University of Guelph In partial fulfilment of requirements for the degree of Doctor of Philosophy in Chemistry Guelph, Ontario, Canada Emily Terada Carlson, August, 2016 ABSTRACT RING-OPENING REACTIONS OF CYCLOPROPANATED HETEROBICYCLIC ALKENES Emily Terada Carlson Advisor: University of Guelph, 2016 Prof. William Tam Synthetic organic chemistry centers around the development of useful reaction sequences. The primary objectives are to improve chemical transformations by making them more efficient and economical, to derive novel compounds and make them widely accessible, and to provide the scientific community with a better understanding of chemical behaviour so that new processes can be applied in the manufacture of similar structures, often with medicinal value. This thesis describes the construction of various novel heterotricyclo[3.2.1.02,4]octanes, and their subsequent ring-opening reactions to afford uniquely functionalized and structurally appealing organic frameworks. The first part of this work concerns the preparation of some common heterobicyclic alkenes and their derivatization by palladium-catalyzed diazocyclopropanation. This produced over 40 novel cyclopropanes with satisfactory yields (64-98%) and complete exo stereoselectivity. A higher equivalency of diazomethane was required to drive the reaction to completion for substrates bearing bulky substituents near the cyclopropanation site. Later portions of this work address transition metal or acid-catalyzed ring-opening reactions of the cyclopropanated heterobicycloalkenes, focusing on 7-oxa and 7- azabenzonorbornadienes. These studies have been subdivided into three types, each providing a unique class of product(s). Type 1 ring-openings led to the formation of cis-1,2-dihydro-2-methylnaphthalenols or polycyclic γ-lactams with facile incorporation of alkyl or aryl nucleophiles from organocuprates. Aromatization could be utilized to convert the dihydronaphthalenols to 2-methylnaphthalenes. Type 2 ring-openings proceeded with thermal acid-catalyzed conditions using alcohol or carboxylic acid nucleophiles, producing 2-(XCH2)naphthalenes (X=RO, RCO2). The reaction rate was found to increase with the acidity of the reaction medium. Type 3 ring-openings were discovered in conjunction with type 2-ring opening studies when bridgehead-substituted cyclopropanated oxabenzonorbornadienes underwent expansion to benzo-fused seven-membered rings. A greater proportion of type 3 product relative to type 2 product was obtained at lower reaction temperatures. Mechanisms for each transformation were supported by intramolecular reactions of cyclopropanated azabenzonorbornadienes under type 1 ring-opening conditions, or by tethered nucleophile-bearing substrates under type 2 and type 3 ring-opening conditions. Thus, several more novel polycyclic lactams, lactones and cyclic ethers were born. As the substrates of this investigation are still largely unexplored, future work in this area is promising. iv Acknowledgments Thank you, William, for your constant support and for making this thesis work possible. Your guidance over the years has given me confidence in my work and helped me ask more critical questions. Thank you Professors Schwan, Manderville and Dmitrienko for being on my Advisory Committee and for encouraging me to think outside the box. To my Examination Committee members whom I am grateful to have the opportunity to meet - Professor Christine Gottardo and Professor Michael Denk - your critique is very much appreciated. Also, thank you William, Adrian, Selim, and Mike for showing me in my undergraduate years that I could pursue my passion in a field that I was a total novice to. To the Tam Group members and friends I’ve had the opportunity to work with - thank you for your patience and willingness to share your knowledge with me. Especially Katrina and Beka: I really couldn’t ask for better lab mates. Thanks for inspiring me with your team efforts, and for organizing events for the group like the escape room or trivia nights, as well as cooking and dinner parties at your place. It’s been really fun. I’d like to thank friends and faculty of the department including Professors Lori Jones, Glenn Penner, Aziz Houmam, and Kate Stuttaford, who have had a strong impact on my early years of chemical education, not to mention former students Mike Sproviero, Chad, Jordan, Stefan, Renee and Neil for being great role models. A special thank you to Linda Allen for shaping my path - I miss you very much. Thanks Rob for all your help in safety and lab techniques and to Wojciech for providing office space to our group in difficult times. Thanks to NMR Centre members Peter, Valerie, Andy and Sameer for sharing your knowledge, to Dr. Wang and Dr. Lough for MS and XRD analysis, and to Dr. Blanchard’s group for providing us with N-O or N- N bicyclic alkenes. Thanks also to the Machine Shop, Electronics Shop, and everyone else who v has helped me along the way, including Aaron, Adam, Erwin and Matt. I am grateful to our department, the University of Guelph and (GWC)2 for providing me with several graduate scholarships, and a wonderful learning environment. Finally, a note to my family and friends: I’d like to thank my parents and Obachama in Japan and my grandparents in Michigan for all their love, and for supporting my choice to study in Canada. Papa, thanks for homeschooling me and fostering my interest in science. 日本を離れ て 8 年間、遠くからえみちゃんの事を見守ってくれて、ありがとう。Grandma and Grandpa, thanks for keeping me company via Skype each weekend, and for letting me visit Vista on the longer breaks. To the Moores and Robertsons, thank you for warmly embracing me, and for introducing me to your fun family traditions. The use of Grumps’ car has also been a big help in the last couple years. Mike, I really can’t thank you enough for being such a loving and understanding Fiancé. We’ve been through a lot together, but your optimism has always kept me going strong. Thanks for listening to me talk about organic chemistry. Also, thanks to the Jugglers of the University of Guelph. Our gatherings and road trips helped punctuate my work so I could return to the lab with even more ambition. A quote from a disputable source says “It is good to have an end to journey toward; but it is the journey that matters, in the end.” My time at the University of Guelph has been a truly rewarding experience, and it will always be a memory that I prize. A sincere thank you to all. vi Table of Contents Table of Contents vi List of Supporting Data and Appendices ix List of Tables x List of Figures xi List of Schemes xii List of Abbreviations and Symbols xviii Chapter 1: Introduction 1.1 - Heterobicycloalkenes 2 1.2 - Ring-Opening Reactions of Oxa- and Azabenzonorbornadienes 4 1.3 - Synthesis of Oxa- and Azabenzonorbornadienes 10 1.3.1 - General Overview 10 1.3.2 - Preparation of Arynes 11 1.3.3 - Preparation of Substituted Furans and Pyrroles 15 1.3.4 - Preparation of Heterobicyclic Alkenes 17 1.4 - Cyclopropanated Heterobicycloalkenes 24 1.4.1 - Research Premise and Hypothesis 24 1.4.2 - Ring Strain and Reactivity of Cyclopropanes 25 1.5 - Summary and Overview 29 1.6 - References 30 vii Chapter 2: Cyclopropanation of Heterobicycloalkenes 2.1 - Introduction 39 2.2 - Palladium-catalyzed Cyclopropanation with Diazomethane 44 2.3 - Results and Discussion 47 2.3.1 - Cyclopropanation of 7-Oxabicycloalkenes 47 2.3.2 - Cyclopropanation of 2-Oxa-3-Azabicyclic and 2,3-Diazabicyclic Alkenes 54 2.3.3 - Cyclopropanation of 7-Azabenzonorbornadienes 56 2.4 - Conclusion 59 2.5 - Experimental 60 2.6 - References 75 Chapter 3: Type 1 Ring-Opening Reactions of Cyclopropanated Oxabenzonorbornadienes with Organocuprates: Synthesis of Dihydronaphthols 3.1 - Introduction 80 3.1.1 - Organocopper Reagents 81 3.2 - Results and Discussion 83 3.3 - Conclusion 98 3.4 - Experimental 98 3.5 - References 112 Chapter 4: Type 2 Ring-Opening Reactions of Cyclopropanated Oxabenzonorbornadienes under Acid Catalysis: Synthesis of Naphthalenes 4.1 - Introduction 116 4.2 - Results and Discussion 118 4.2.1 - Alcohol Nucleophiles 118 4.2.2 - Carboxylic Acid Nucleophiles 123 4.3 - Conclusion 134 4.4 - Experimental 135 4.5 - References 146 viii Chapter 5: Type 3 Ring-Opening Reactions of Cyclopropanated Oxabenzonorbornadienes: Synthesis of 7-Membered Rings 5.1 - Introduction 150 5.1.1 - Cycloadditions 151 5.1.2 - Ring-closing Metathesis 153 5.1.3 - Ring-expansions and Rearrangements 154 5.1.4 - Type 3 Ring-opening Reactions of Cyclopropanated Oxabenzonorbornadienes 157 5.2 - Results and Discussion 158 5.3 - Conclusion 169 5.4 - Experimental 170 5.5 - References 179 Chapter 6: Tandem Ring-Opening and Intramolecular Ring-Closure Reactions of Cyclopropanated Azabenzonorbornadienes 6.1 - Introduction 184 6.2 - Results and Discussion 184 6.2.1 - Reactions using Organocuprates 184 6.2.2 - Reactions using Acid Catalysts 194 6.3 - Conclusion 195 6.4 - Experimental 196 6.5 - References 203 Chapter 7: Intramolecular Reactions of Cyclopropanated Oxabenzonorbornadienes 7.1 - Introduction 206 7.2 - Results and Discussion 207 7.3 - Conclusion 212 7.4 - Experimental 212 7.5 - References 216 ix Chapter 8: Prospective 8.1 - Introduction 218 8.2 - Future Work 219 8.3 - Conclusion 224 8.4 - Experimental 224 8.5 - References 226 List of Supporting Data and Appendices Appendix A: Representative NMR Spectra Chapter 2: compounds 2.10w, 2.24, 2.26l 229 Chapter 3: compounds 3.2a, 3.3a, 3.5, 3.25a and 3.25b 234 Chapter 4: compounds 4.2k, 4.11, 4.3i, 4.3p 241 Chapter 5: compounds 5.22a, 5.23a, and 5.28 246 Chapter 6: compound 6.3a 249 Chapter 7: compounds 7.9 and 7.10 250 Chapter 8: compound 8.2 252 Appendix B: X-ray Data Chapter 2: compound 2.10t 253 Chapter 5: compound 5.23a 263 x List of Tables Table 2.1 Former cyclopropanation attempts of 7-oxabenzonorbornadiene 2.9a.
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