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Palladium-Mediated CH Activations

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Palladium-Mediated CH Activations Palladium-Mediated C-H Activations DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By William Howell Henderson Graduate Program in Chemistry The Ohio State University 2011 Dissertation Committee: Professor James P. Stambuli, Advisor Professor Dennis Bong Professor Craig Forsyth Copyright by William Howell Henderson 2011 Abstract A selective allylic oxidation of terminal alkenes using novel alkyl aryl sulfides as ligands for Pd(OAc) 2 was developed, which allows for lower catalyst loadings and significantly decreased reaction times. Reactions utilizing alkyl aryl sulfide ligands selectively provide the linear allylic acetates in yields comparable to previously reported methods. Additionally, a greener method allowing for the use of oxygen as the stoichiometric oxidant is also reported. Attempts to isolate intermediate complexes led to isolable palladium chloride complexes, but no diacetate complexes could be isolated as pure compounds. Mechanistic studies conducted allude to an acetoxypalladation mechanism rather than a mechanism containing π-allyl palladium intermediates. 1 Typically, allylic oxidations of internal alkenes either fail to provide any allylic oxidation products or provide a mixture of allylic acetate isomers. The previously mentioned methodology has led to the discovery that cis -vinylsilanes, in the absence of external ligand, undergo allylic oxidations to provide branched allylic acetate trans - vinylsilane as the sole diastereomer and regioisomer. Attempting to apply the allylic oxidations to other internal alkenes it was discovered that vinyl fluorides and alkyl enol ethers form α,β-unsaturated aldehydes in good yields requiring low loadings (1-5 mol %) of Pd(OAc) 2. Previously reported Saegusa oxidations utilize anywhere from 0.5-1 equivalent of Pd(OAc) 2 to form α,β-unsaturated aldehydes and ketones. A modification reported by Larock uses 10 mol % Pd(OAc) 2, however, DMSO is used as a solvent and ii reactions require up to 3 days to proceed to completion. This new method tolerates a broad range of functional groups. Initial mechanistic studies of this new catalyst system were undertaken. Palladium acetate has been shown to form a novel palladacycle with tri-tert - butylphosphine through a facile room temperature C-H activation. This palladacycle is stable to reduction to Pd(0) species under typical aryl-amination conditions requiring base and amine. As a result, coordinated tri-tert -butylphosphine is easily displaced by less basic phosphines and even secondary amines. The kinetic stability of this complex indicates that it is likely a catalyst decomposition product rather than a predominant catalytic intermediate and as a result formation of this complex likely inhibits quantitative formation of active catalytic intermediates. 2 iii Dedication This document is dedicated to my family and friends. iv Acknowledgments I would like to thank all of The Stambuli Research Group members as well as other students in the department for all of their help during my graduate school career. Dr. Nicolas Proust was a fantastic post-doc to have around the lab. He was interested in answering questions and solving problems within the group and thoroughly enjoyed talking about chemistry and ongoing projects. He was one of my favorite people to talk to about research and I am lucky to have worked with him on a couple of projects. In addition, he may be the best editor/reviewer I have ever worked with. Dr. Chad Eichman was an integral part of my graduate Ph.D. He was always someone I could bounce ideas off of and made lab work manageable. I spent more hours in lab with him than any other person. He is the only person that could make it through 24 h of lab with me. Honestly, he is a great friend and colleague. Also, as a senior member of our group Dr. Carla Councellor was always helpful and made joining a new group much easier. Kamala was always willing to help me whenever I asked, and was kind enough to give me rides to my house when it was freezing outside. She has reviewed and edited every document I have produced over the last year since Nico and Chad have left. I would also like to thank Kamala, Sean, Check, Chip and Lauer for all of the discussions and help in lab as well as financial support during tough times when all I had was a v useless American Express credit card. Check and Lauer are great people to work with on projects and as bothersome as I was, Matheiu never hesitated to help me with any computer problems or read any document, no matter how busy he looked. Brenda was kind enough to make a cheesecake every year for my birthday. With regards to friends from home, Justin Jones is the best friend I could have asked for. Though not in Columbus, he made sure to clear his schedule so that he had time to go fishing every time I visited Richmond and made an effort just to call and say hi regularly. Carrie supported me through most of my graduate career and some of the toughest times. She was an incredible girlfriend and I am grateful for every minute we spent together. Veronica is always great at giving advice and provided me with insight into life after graduate school. The help she has given me is priceless. All of my friends, including Christine, Pritesh, Chris, Jeff Brad, Ryan, Fraser, and Colin, are also great friends to have and made visiting home something to look forward to every vacation. I appreciate the support my family has given me including my sister and brother. Additionally, my mother and father have been extremely supportive in every endeavor that I have undertaken. If I told my mother I was going to the moon she would probably tell me he believed I could make it. I love them all. Most importantly, I would like to thank my advisor, James Stambuli, for allowing me to learn and perform research in The Stambuli Research Group. Over my graduate career he has taught me how to approach problems, pay attention to detail, and think critically. Being one of the first students to join his group was tough, but I can honestly vi say that it was an incredible experience. I am certain that under his instruction and with his help all of his students will be successful in their future endeavors. Lastly, I would like to thank the other professors and staff at The Ohio State University for their instruction, guidance, and help. Dr. Tanya Young entrusted me with maintaining the NMR facilities which was a welcome break from teaching. I would especially like to thank Professor Craig Foryth and Professor Dennis Bong for serving on my dissertation committee, vii Vita September 10, 1984 ....................................... Born – Richmond, Virginia May 2006....................................................... B.S. Chemistry, Virginia Polytechnic Institute and State University August 2006 – March 2010 ........................... Graduate Teaching Assistant The Ohio State University March 2010 to present .................................. Graduate NMR Facilities Assistant The Ohio State University Publications Henderson, W. H.; Alvarez, J.: Eichman, C. C.; Stambuli, J. P. “Characterization, Reactivity and Potential Catalytic Intermediacy of a Cyclometalated Tri-tert- butylphosphine Palladium Acetate Complex” Organometallics , 2011 , 30 , 5038. Check, C. T.; Henderson, W. H.; Vanden Eynden, M.: Stambuli, J. P. “Regio- and Stereoselective Silyl-Directed C-H Allylic Oxidations of Olefins” J. Am. Chem. Soc. 2011 Submitted. viii Henderson, W. H.; Check, C. T.; Proust, N.; Stambuli, J. P. “Allylic Oxidations of Olefins Using a Palladium Thioether Catalyst” Org. Lett. 2010 , 12 (4), 824. Henderson, W. H.; Stambuli, J. P. “Lithium 2,2,2-Trifluoroethoxide” EROS 2009 . Fields of Study Major Field: Chemistry ix Table of Contents Abstract ............................................................................................................................... ii Dedication .......................................................................................................................... iv Acknowledgments ............................................................................................................... v Vita ................................................................................................................................... viii Publications ...................................................................................................................... viii Fields of Study ................................................................................................................... ix Table of Contents ................................................................................................................ x List of Tables .................................................................................................................... xiii List of Figures ................................................................................................................... xv List of Schemes ............................................................................................................... xvii List of Abbreviations ......................................................................................................... xx Chapter 1: Introduction ....................................................................................................... 1 1.1 Early Reports of Allylic Oxidations ....................................................................
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