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Palladium-Catalyzed Reactions of Ammonia, Carbon Monoxide, and Cyanide

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Palladium-Catalyzed Reactions of Ammonia, Carbon Monoxide, and Cyanide PALLADIUM-CATALYZED REACTIONS OF AMMONIA, CARBON MONOXIDE, AND CYANIDE BY JESSICA LOUISE KLINKENBERG DISSERTATION Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemistry in the Graduate College of the University of Illinois at Urbana-Champaign, 2012 Urbana, Illinois Doctoral Committee: Professor John F. Hartwig, Chair Professor Scott E. Denmark Professor Gregory S. Girolami Professor Thomas B. Rauchfuss ABSTRACT The reductive eliminations of primary arylamines from a series of bisphosphine-ligated arylpalladium(II) parent amido complexes countered several established trends. In contrast to arylamido and alkylamido complexes of the aromatic bisphosphines DPPF and BINAP, parent amido complexes did not form or undergo reductive elimination of monoarylamines. However, arylpalladium parent amido complexes ligated by the alkylbisphosphine CyPF-t-Bu formed in good yield and underwent reductive elimination. Despite the basicity of parent amido ligand and the typically faster reductive elimination from complexes containing more basic amido ligands, the CyPF-t-Bu-ligated arylpalladium parent amido complexes underwent reductive elimination much more slowly than the analogous complexes containing arylamido or alkylamido ligands. Moreover, the parent amido complexes formed more rapidly and are more stable thermodynamically in a series of exchange processes than the arylamido complexes. Computational studies supported the overriding influence of steric effects on the stability and reactivity of the parent amido complex. The slow rate of reductive elimination caused the arylpalladium amido complex to be the resting state of the coupling of aryl halides with ammonia catalyzed by CyPF-t-Bu-ligated palladium, and this resting state contrasted the Pd(0) or arylpalladium(II) resting states of reactions of aryl halides with amines catalyzed by most palladium complexes. CyPF-t-Bu-ligated palladium complexes also catalyzed the aminocarbonylation of aryl bromides and aryl iodides with ammonia and carbon monoxide. Primary benzamides formed in good yields from aryl bromides and aryl iodides with 2 mol % of Pd[P( o-tol) 3]2 and CyPF-t-Bu under 3 atm total of ammonia and carbon monoxide. The resting state of the catalyst was identified as the Pd(0) di-carbonyl complex (CyPF-t-Bu)Pd(CO) 2, which dimerized to [(CyPF-t- ii Bu) 2Pd 2(µ-CO)] upon isolation. These complexes did not undergo oxidative addition of aryl chlorides and aryl tosylates. The effect of added CO on the oxidative addition steps was demonstrated. In addition, the intermediacy of an arylpalladium acyl complex in the formation of the benzamide products was demonstrated. A method for the palladium-catalyzed cyanation of aryl chlorides and aryl tosylates was developed. The catalyst formed from the combination of Pd[P( o-tol) 3]2 and CyPF-t-Bu formed aryl nitriles via reaction with Zn(CN) 2 in high yields with an unprecedented catalyst loadings of 0.8-1 mol %. LiCl was shown to influence the transmetalation of arylpalladium chloride complexes with Zn(CN) 2. In addition, the isolation and characterization of arylpalladium cyanide complexes that undergo reductive elimination to form arylnitriles have been demonstrated. The rates of reductive elimination from a series of arylpalladium cyanide complexes reveal that the electronic effects on the reductive elimination from arylpalladium cyanide complexes are distinct from those on reductive eliminations from arylpalladium alkoxo, amido, thiolate, and enolate complexes. Arylpalladium cyanide complexes containing aryl ligands with electron-donating substituents undergo faster reductive elimination of aromatic nitriles than complexes containing aryl ligands with electron-withdrawing substituents. In addition, the transition state for the reductive elimination of the aromatic nitrile is much different from that for reductive eliminations that occur from most other arylpalladium complexes. Computational studies indicate that the reductive elimination of an arylnitrile from Pd(II) occurs through a transition state more closely related in structure and electronic distribution to that for the insertion of CO into a palladium-aryl bond. iii To My Grandma “Niti” iv ACKNOWLEDGMENTS Getting to this point in my graduate school career has been quite an endeavor, and I have a number of people to thank for helping me through. First off, my advisor, Prof. John Hartwig, has been the greatest model of a scientist and a scholar. It has never ceased to amaze me how much knowledge he retains, and how good he is at everything we see him do. He passes his skills on to his students, and by the time we are ready to leave, we can design and execute experiments, give insightful research talks, and identify dangling modifiers better than most English majors. Simply, I have learned so, so much from John. I am forever grateful to have worked with such a talented group of people in the Hartwig lab. I was able to develop strong friendships with “the Yale students” Dr. Jackie Murphy (now Murphy-Knight!), Dr. Mark Pouy, and Dr. Giang Vo. Their encouragement has been instrumental to developing my self-confidence as a scientist, and I’m not sure where I would be today if I hadn’t had such great mentors from the very beginning. Thank you all for the laughs, the beers, and the Friday night pie-eating sessions. You kept me grounded and positive! I am also thankful for the small bit of our group at Illinois that’s held together for the last 9 months or so. It hasn’t been easy with the stress of the lab move and the pressure of finishing up, but we’ve kept both our spirits and our production high! It is a simple truth that I would never have gotten through five years of graduate school without my family. My dad once threatened to drive all 400 some-odd miles to Illinois just to “kick some sense into” me when I tried to quit for probably the fifth time. My mom made the trek a number of times as well, and we’ve shared some great times together in this state. She even did the Illinois marathon with me, walking the half in under 3 hours! Through the late-night distress calls (“I can’t possibly go on!”) to the early morning wake-ups (“I got an NSF v Fellowship!”), mom and dad have always been my steadfast support on the other end of the line. And up until her death late in my third year, my grandma, Juanita, was by far my loudest cheerleader. I am fairly certain that the entire city of Mayfield Heights, Ohio knows about Jessica Klinkenberg, if only because Grandma couldn’t keep quiet about any of my accomplishments. I dedicate this dissertation to her. I still really miss trying to explain to her exactly why I study transition metal-catalyzed reactions during our weekly Sunday chats. But I didn’t come to Illinois alone. My fiancé, Matt, started at the U of I before I finished my undergraduate career, and I followed him here. At that time, I wasn’t sure we’d make it as far as we have, but he has been the only consistently good thing in my life here in Champaign- Urbana. From biking centuries and running marathons to drowning our sorrows in a bottle of cabernet sauvignon, Matt hasn’t left my side. Special thanks go to my close friends Matt Small and Mica Swyers. Small and I have covered more miles in Central Illinois than most people would believe, and he is always up for a 3 hour bike ride. Mica found me through a facebook search of our alma mater, the University of Virginia, and we’ve been close friends since our introduction in 2008. We lick frosting off spoons and order Chinese food, and after a few hours of shooting the breeze, all is right with the world. vi TABLE OF CONTENTS Chapter 1. Overview of Transition Metal-Catalyzed Reactions of Ammonia, Carbon Monoxide, and Cyanide to form Carbon-Heteroatom and Carbon-Carbon Bonds……………......................1 1.1. Introduction………………………………………………………………………………….1 1.2. Overview of Homogeneous, Transition Metal-Catalyzed Reactions with Ammonia……………………………………………………………………………………...3 1.2.1. Reactions in which the catalysts tolerate the presence of ammonia…………………...4 1.2.1.1. Hydroaminomethylation…………………………………………………………5 1.2.1.2. Reductive amination of ketones…………………………………………………7 1.2.1.3. Alkylation of ammonia with alcohols……………………………………………9 1.2.2. Catalytic reactions of ammonia occurring without direct coordination to the metal…11 1.2.2.1. Allylic substitution or telomerization…………………………………………...12 1.2.2.2. Hydroamination with ammonia…………………………………………………14 1.2.3. Catalytic reactions of ammonia occurring through metal-amido complexes…………16 1.2.3.1. Palladium-catalyzed coupling of ammonia with aryl halides…………………..17 1.2.3.2. Copper-catalyzed coupling of ammonia with aryl halides and boronic acids…………………………………………………………………….20 1.2.4. Summary………………………………………………………………………………24 1.3. Overview of Carbonylative Cross-Coupling Reactions…………………………………….25 1.3.1. Alkoxycarbonylation………………………………………………………………….26 1.3.2. Aminocarbonylation…………………………………………………………………..27 1.3.3. Carbonylative variants of classic cross-coupling reactions to form ketones 1.3.3.1. Carbonylative Heck……………………………………………………………..33 vii 1.3.3.2. Carbonylative Suzuki…………………………………………………………...34 1.3.3.3. Carbonylative Negishi…………………………………………………………..35 1.3.4. Summary………………………………………………………………………………36 1.4. Overview of Palladium-Catalyzed Cyanation Reactions…………………………………...37 1.4.1. Non-catalytic and stoichiometric, metal-mediated preparation of benzonitriles……………………………………………………………….38 1.4.2. Non-palladium-catalyzed cyanation methods………………………………………...39 1.4.3. Palladium-catalyzed cyanation of aryl halides………………………………………..39 1.4.3.1. NaCN or KCN cyanide sources………………………………………………...40 1.4.3.2. Reactions with Zn(CN) 2………………………………………………………...42 1.4.3.3. Reactions with K 4[Fe(CN) 6]…………………………………………………….43 1.4.3.4. Reactions with other cyanide sources…………………………………………...44 1.4.3.5. Mechanistic considerations……………………………………………………...45 1.4.4. Summary………………………………………………………………………………47 References………………………………………………………………………………………..48 Chapter 2. Slow Reductive Elimination of Arylpalladium Parent Amido Complexes...………...52 2.1.
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