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The Nickel-Catalyzed Mizoroki–Heck Reaction: High Regioselectivity in Olefin Migratory Insertion and Photoredox- Enabled Indoline Formation

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The Nickel-Catalyzed Mizoroki–Heck Reaction: High Regioselectivity in Olefin Migratory Insertion and Photoredox- Enabled Indoline Formation The Nickel-Catalyzed Mizoroki–Heck Reaction: High Regioselectivity in Olefin Migratory Insertion and Photoredox- Enabled Indoline Formation by Sarah Z. Tasker B.Sc. Chemistry, with Honors Calvin College, 2010 SUBMITTED TO THE DEPARTMENT OF CHEMISTRY IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY IN ORGANIC CHEMISTRY at the MASSACHUSETTS INSTITUTE OF TECHNOLOGY September 2015 © 2015 Massachusetts Institute of Technology All rights reserved The author hereby grants to MIT permission to reproduce and to distribute publicly paper and electronic copies of this thesis document in whole or in part in any medium now known or hereafter created. Signature of Author _____________________________________________________________ Department of Chemistry July 7, 2015 Certified by ___________________________________________________________________ Timothy F. Jamison Professor of Chemistry Thesis Supervisor Accepted by ___________________________________________________________________ Robert W. Field Chair, Department Committee on Graduate Students This doctoral thesis has been examined by a committee in the Department of Chemistry as follows: Professor Rick L. Danheiser ______________________________________________________ Thesis Chair Professor Timothy F. Jamison _____________________________________________________ Thesis Supervisor Professor Timothy M. Swager _____________________________________________________ 2 For my family 3 4 The Nickel-Catalyzed Mizoroki–Heck Reaction: High Regioselectivity in Olefin Migratory Insertion and Photoredox- Enabled Indoline Formation by Sarah Z. Tasker Submitted to the Department of Chemistry on July 7, 2015 in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in Organic Chemistry ABSTRACT Achieving high selectivity in the Heck reaction of electronically unbiased alkenes has been a longstanding challenge. Using a nickel-catalyzed cationic Heck reaction, we were able to achieve excellent selectivity for branched products (≥19:1 in all cases) over a wide range of aryl electrophiles and aliphatic olefins. A bidentate ligand with a suitable bite angle and steric profile was key to obtaining high branched/linear selectivity, while the appropriate base suppressed alkene isomerization of the product. Though aryl triflates are traditionally used to access the cationic Heck pathway, we have shown that by using triethylsilyl trifluoromethanesulfonate we can effect a counterion exchange of the catalytic nickel complex such that cheaper and more stable aryl chlorides, mesylates, tosylates, and sulfamates can be used to yield the same branched products with high selectivity. 5 Nickel/photoredox catalysis is used to synthesize indolines in one step from iodoacetanilides and alkenes. Very high regioselectivity for 3-substituted indoline products is obtained for both aliphatic and styrenyl olefins. Mechanistic investigations indicate that oxidation to Ni(III) is necessary to perform the difficult C–N bond-forming reductive elimination, producing a Ni(I) complex which in turn is reduced to Ni(0). This process serves to further demonstrate the utility of photoredox catalysts as controlled single electron transfer agents in multi-oxidation state nickel catalysis. Thesis Supervisor: Timothy F. Jamison Title: Professor of Chemistry 6 Portions of this thesis have been published in the following articles co-written by the author and have been reprinted and/or adapted with permission from their respective publishers. Nickel-Catalyzed Mizoroki–Heck Reaction of Aryl Sulfonates and Chlorides with Electronically Unbiased Terminal Olefins: High Selectivity for Branched Products. Tasker, S. Z.; Gutierrez, A. C.; Jamison, T. F. Angew. Chem., Int. Ed. 2014, 53, 1858– 1861. DOI: 10.1002/anie.201308391. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. A.C.G. performed initial ligand screening experiments. S.Z.T. optimized the reaction conditions, and carried out screening, scope and mechanistic experiments. Recent Advances in Homogeneous Nickel Catalysis Tasker, S. Z.†; Standley, E. A.†; Jamison, T. F. Nature 2014, 509, 299–309. DOI: 10.1038/nature13274. Copyright © 2014 Nature Publishing Group. S.Z.T. and E.A.S. worked together to outline and write the content, and T.F.J. helped edit the manuscript, references and figures. Highly Regioselective Indoline Synthesis under Nickel/Photoredox Dual Catalysis Tasker, S. Z.; Jamison, T. F. J. Am. Chem. Soc. 2015, [Online early access]. Published Online: July 21, 2015. DOI: 10.1021/jacs.5b05597. Copyright © 2014 American Chemical Society. All synthetic work was carried out by S.Z.T. Peter Müller (Director, Diffraction Facility of MIT Department of Chemistry) carried out the single-crystal X-ray diffraction experiments. †These authors contributed equally to this work. 7 8 Acknowledgments My time at MIT has been an amazing time of both scientific and personal growth. Although some parts have been challenging, I would not have made any other decision than to pursue my Ph.D. in this department. Of course, I could never have gotten so far without the help and support of an incredible number of people, whom I would like to briefly thank here. My early interest in science was fostered by my parents, who encouraged me to run around outside, read voraciously and pursue my interests. My teachers at Westview Elementary and Roosevelt Junior High in Zanesville, Ohio, though the school district was of modest means, fought to challenge me, allowing me to skip ahead in math, paying for summer camps, and sending me to an amazing Talented and Gifted program once a week. There, we played Oregon Trail, created and filmed plays about the Civil War, learned how to use a card catalog, and made up languages. Perhaps the most important experiences that set me on the path that I’m on today occurred during my time at Calvin College. I entered as a biology major, and took Organic Chemistry as my very first class to “get it out of the way”. However, I immediately loved the elegance and challenge of organic synthesis and learning about the fundamentals of reaction mechanisms. I am so thankful that my two professors in organic chemistry, Prof. Carolyn Anderson and Prof. Chad Tatko saw my interest and (strongly) encouraged me to change majors and come do research in their labs during the school year and summer. Carolyn in particular has become an incredible mentor, and taught me innumerable things: proper reaction techniques, methodology design, career planning, leadership, and much more. I also credit any skills in scientific writing and presenting that I may have to her and to my other professors at Calvin. Both Chad and Carolyn also gave me the opportunity to travel to national meetings to give posters on my research and hear talks from prominent chemists. I also want to thank all my chemistry professors at Calvin for giving me a well-rounded foundation in all disciplines of chemistry. When choosing graduate schools, I was drawn to MIT for its strong academic department and sense of community among the graduate students I met. I could not have made a better choice than to come here and to choose Prof. Tim Jamison as my advisor. Tim has been incredibly supportive, open, and thoughtful in both chemistry and other aspects of graduate school. I have learned so much from his example and ideas, while he has also trusted me with the space and freedom to develop my own ideas and ownership of my chemistry. I appreciate the focus Tim places on the development of all aspects of successful chemists, from setting team synthesis challenges, to painstakingly going over job talks of group members slide-by-slide, to setting up mentoring relationships in the lab. 9 My coworkers in the Jamison lab have also been exemplary through all the years that I have worked alongside them. Everyone is always willing to drop what they’re doing to help out in any way they can. In particular, I would like to thank Dr. Alicia Gutierrez and Dr. Matt Beaver for being amazing mentors and friends during my early graduate career, helping with everything from Schlenk line techniques, to reaction troubleshooting, to career advice. My two fellow fifth years, (now Dr.) Eric Standley and (soon to be Dr.) Toma Halkina have been sources of both fun and commiseration throughout the years. I have also enjoyed collaborating with Eric on three review articles on nickel chemistry that I think will be an important legacy, and he has even put up with my grammatical nitpicking with remarkable patience! I would also like to thank the rest of “Team Nickel” for helpful discussions and interesting ideas: Dr. Jeff Byers, Dr. Kim Jensen, and Dennis Nielsen. I feel fortunate to leave my current projects in the capable hands of Jessica Weber. Many other group members have spent time in the Jamison lab during my time here, and I unfortunately do not have room (or my readers the patience) to thank all of them, but I would also like to call out Dr. Kurt Armbrust for his knowledge and dedication to leading the lab, and to Dr. Matt Katcher for help reading drafts and refining my scientific ideas. Outside of the Jamison lab, I also am grateful to many others in the department. First of all, Prof. Rick Danheiser has been a conscientious and invested Thesis Chair, with whom I have had many helpful discussions. He and Dr. Beth Vogel Taylor both gave me the opportunity to improve my teaching skills by assisting in graduate and undergraduate organic chemistry classes above and beyond the typical teaching requirements. There are also several technical aspects of my thesis work with which I had assistance. Dr. Peter Müller obtained and interpreted the two crystal structures and Li Li and Eric obtained the HRMS values that appear herein. I would also like to thank the Surendranath lab, and Megan Jackson and Anna Wuttig in particular, for teaching me how to do cyclic voltammetry experiments, and answering all of my naïve questions. Finally, I would like to thank Prof. Brad Pentelute and his lab for our nascent collaboration, which unfortunately I was not able to include here. Another important part of my graduate experience has been with the ChemREFS student group.
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