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Deoxygenation Supplemental Without Spectra Novel Organic Transformations Arising from Gold(I) Chemistry By Mathieu André Morin Thesis submitted to the faculty of Graduate and Postdoctoral Studies In partial fulfillment of the requirements for the Ph.D. degree in chemistry Candidate Supervisor Mathieu André Morin Dr. Louis Barriault Ottawa-Carleton Chemistry Institute Faculty of Science University of Ottawa © Mathieu André Morin, Ottawa, Canada, 2017 Abstract The use of gold in organic chemistry is a relatively recent occurrence. In addition to being previously considered too expensive, it was also believed to be chemically inert. Soon after the early reports indicating its rich reactivity, the number of reports on chemical transformations involving gold sky rocketed. One such report by Toste and coworkers demonstrated the intramolecular addition of silyl enol ether onto Au(I) activated alkynes, resulting in a 5-exo dig cyclization. The first part (Chapter 1) of this thesis discusses the development of a Au(I) catalyzed polycyclization reaction inspired by this transformation. The reaction demonstrated the ability of Au(I) to successfully catalyze the formation of multiple C-C bonds and resulted in the synthesis of benzothiophenes, benzofurans, carbazoles and hydrindene. With the current resurgence of photochemical transformations being reported in literature, various opportunities for the use of Au(I) complexes arose. The substantial relativistic effect observed in gold which make it a good soft Lewis acid also has a significant influence on the redox potential of this metal. Chapter 3 of this thesis discusses the development of a Au(I) photocatalyzed process which benefits from having both a strong oxidation and reduction potential for the reduction of carbon-halide bonds. Radical reductions and cyclizations were accessed with the use of polynuclear Au(I) photocatalysts. In depth analysis of catalytically active Au(I) complexes helped elucidate the mechanism by which this photochemical reaction occurs. This part (Chapter 4) also covers serendipitously discovered uncatalyzed photochemical transformations derived from our work with gold. The halogenation reaction of primary alcohols was successfully achieved and a combination of our developed methods resulted in an efficient dehydroxylation protocol. II Acknowledgement The time spent working towards this thesis has allowed me the pleasure of interacting with many people who have made this an enriching experience and without whose support this final product would not have been possible. I would like to first thank Prof. Louis Barriault for bringing me into the realm of chemical research. The guidance and experience I have received under his mentorship have been essential to my development as an organic chemist. I am very grateful for his willingness to place such confidence in me and allow me the freedom to pursue this new branch of chemistry with the lab. I would also like to thank Prof. Derek Pratt for answering my many questions about chemistry. The amount of knowledge he shared with me, especially during the first years of my Ph. D. has been instrumental in solidifying my understanding of chemistry. Merci à mes parents, Eric et Solange pour leur amour et support pendant toutes ces années. Malgré la distance ils ont toujours été présents en temps de besoin et ont toujours cru en moi. I would like to thank numerous people both within and outside the lab for their friendship and support; Patrick Levesque for being both a wonderful teacher in the ways of chemistry and a great roommate for several years. Terry McCallum who I was fortunate enough to share many publications and many beers, I am incredibly grateful to have you as a friend and colleague. Gabriel Bellavance for great conversation both about chemistry and literally everything else (I will get to εars….). Philippe εcGee who I was lucky enough to know since my undergraduate studies, who has enriched my experiences in chemistry and taught me so much. Thank you to the III many people I have interacted with throughout these many years, Spencer, J-P, Guillaume, David, Frank, Jason, Joel, Travis, Alex, Colombe, Amandine, Laurie-Anne, Julie, Mike, Huy, Sam. From outside the lab I would like to thank my friends who had to sometimes remind me that I could talk about things other than chemistry. Jenn, Alex, Dré, J.R., Angie, Gen and Vince, with whom I have shared many great nights and stories. Thank you Alyssa for your love and patience when I go on about chemistry, I am grateful to have you in my life. IV Contributions to Research Refereed Publications: Tran, H.; McCallum, T.; Morin, M.; Barriault, δ*. ‘‘Homocoupling of Iodoarenes and Bromoalkanes Using Photoredox Gold Catalysis: A Light Enabled Au(III) Reductive Elimination’’ Org. Lett. (2016) 4308 – 4311 McTiernan, S. D.; Morin, M.; εcCallum, T.; Scaiano, J.C.*; Barriault, δ.* ‘‘Polynuclear Gold (I) Complexes in Photoredox Catalysis: Understanding their Reactivity through Characterization and Kinetic Analysis’’ Catal. Sci. Technol. (2016) 201 – 207 McCallum, T.; Slavko, E.; Morin, M.; Barriault, δ.*; ‘‘Light-Mediated deoxygenation of alcohols with a Dimeric Gold Catalyst’’ Euro. J. Org. Chem. (2015) 81 – 85 Revol, G.; McCallum, T.; Morin, M.; Gagosz, F.*; Barriault, L.*; Photoredox Transformations with Dimeric Gold Complexes, Angew. Chem. Int. Ed. (2013),13342 – 13345 Morin, M.; Levesque, P.; Barriault, L.*; Gold(I)-catalyzed domino cyclization for the synthesis of polyaromatic heterocycles, Beilstein J. Org. Chem. (2013) 2625 – 2628 Contributing Author: Barriault, L.; Morin, M. (2016) ‘‘The σazarov Cyclization of Cross-Conjugated Ketones’’, Cross Conjugation: Modern Dendralene, Radialene and Fulvene Chemistry, Wiley-VCH (Eds. Hopf, H.; Sherburn, M. ISBN: 978-3-527-33437-7) Oral Presentations: Revol, G.; McCallum, T.; Morin, M.*; Gagosz, F.; Barriault, δ. (2013) ‘‘Photoredox Transformations with Dimeric Gold Complexes’’ Centre for Catalysis Research and Innovation (Regional) Poster Presentations: Morin, M.*; εcCallum, T.; Barriault, δ. (2016) ‘‘εethylating with εethanol’’ Gordon Research Conference; Natural Products & Bioactive Compounds (International) Morin, M.*; εcCallum, T.; Barriault, δ. (2015) ‘‘δight Initiated Cascade Reaction for the Synthesis of Polycyclic Compounds’’ International Chemical Congress of Pacific Basin Societies (International) V Morin, M.*; McCallum, T.; Barriault, δ. (2015) ‘‘δight Initiated Radical Polycylization of Cyclopropyl Containing Compounds’’ 98th Canadian Chemistry Conference and Exhibition (International) Morin, M.*; εcCallum, T.; Barriault, δ. (2014) ‘‘Photo-Activated Gold Catalysts: Bridging Bis-Phosphine and Bis-Carbene δigands’’ 19th International Symposium on Homogeneous Catalysis (International) Morin, M.*; εcCallum, T.; Barriault, δ. (2013) ‘‘Photo-Activated Gold Catalysts: Light εediated SET for Radical Formation’’ 6th Pacific Symposium on Radical Chemistry (International) Morin, M.*; δevesque, P.; Barriault, δ. (2012) ‘‘Heterocycle Synthesis via Au(I)/ Prins cyclisation and efforts towards synthesis of dihydrojunenol’’ Synthesis Day, Université d’Ottawa (Regional) Morin, M.*; Levesque, P.; Barriault, L. (2011) ‘‘Synthèse d’hétérocycles par une cascade Au(I)/cyclisation Prins’’ 23e Colloque de Chimie de Sherbrooke (Provincial) VI Table of Contents Details of Contribution .......................................................................................... XV Introduction .......................................................................................................... 1 1.1 Relativistic Effect ............................................................................................................. 3 1.2 Catalysis by Gold(I) Complex.......................................................................................... 4 1.3 Initial Contributions in Au(I) Chemistry ........................................................................ 10 Organic Photochemistry and Photocatalysis ..................................................... 17 2.1. Photochemical Excitation ............................................................................................... 17 2.2. Photocatalysis ................................................................................................................. 19 2.3. Photocatalytic Systems ................................................................................................... 21 2.3.1. Single catalyst systems ........................................................................................................ 21 2.3.2. Dual catalytic photochemical processes .............................................................................. 25 Bi-nuclear Au(I) Photocatalysis ........................................................................ 32 3.1 Au2dppm2Cl2 .................................................................................................................. 32 3.2 Photocatalyzed Reduction of Halocarbon Bonds ........................................................... 34 3.2.1 Reduction of unactivated bromoalkanes ............................................................................. 36 3.2.2 Reduction of bromoarenes .................................................................................................. 38 3.2.3 Photocatalyzed intermolecular radical addition .................................................................. 40 3.3 Further Development of Au(I) Photochemical Reduction ............................................. 42 3.4 Mechanistic Investigation .............................................................................................
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