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I. Mechanistic Studies of a Copper-Catalyzed Electrophilic Amination of Diorganozinc Reagents by O-Benzoyl N,N-Dialkylhydroxylamines

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I. Mechanistic Studies of a Copper-Catalyzed Electrophilic Amination of Diorganozinc Reagents by O-Benzoyl N,N-Dialkylhydroxylamines I. MECHANISTIC STUDIES OF A COPPER-CATALYZED ELECTROPHILIC AMINATION OF DIORGANOZINC REAGENTS BY O-BENZOYL N,N-DIALKYLHYDROXYLAMINES II. DEVELOPMENT OF A 3-EXO-DIG CYCLIZATION FOR THE PREPARATION OF VINYLIDENE CYCLOPROPANES III. TOTAL SYNTHESIS OF (+)-POLYANTHELLIN A Matthew James Campbell A dissertation submitted to the faculty of the University of North Carolina at Chapel Hill in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Department of Chemistry Chapel Hill 2009 Approved by: Jeffrey S. Johnson Erik J. Alexanian Maurice S. Brookhart Joseph L. Templeton Cynthia K. Schauer © 2009 Matthew James Campbell ALL RIGHTS RESERVED ii ABSTRACT MATTHEW JAMES CAMPBELL: I. Mechanistic Studies of a Copper-Catalyzed Electrophilic Amination of Diorganozinc Reagents by O-Benzoyl N,N-Dialkylhydroxylamines II. Development of a 3-Exo-Dig Cyclization for the Preparation of Vinylidene Cyclopropanes III. Total Synthesis of (+)-Polyanthellin A (Under the direction of Professor Jeffrey Scott Johnson) I. Mechanistic Studies of a Copper-Catalyzed Electrophilic Amination of Diorganozinc Reagents by O-Benzoyl N,N-Dialkylhydroxylamines The mechanism of the Cu-catalyzed amination of R2Zn reagents by O-benzoyl N,N-dialkylhydroxylamines has been investigated. An SN2 pathway has been supported because : (i) stoichiometrically generated cuprates were used to prove zinc is not essential in the C–N bond forming step; (ii) the configuration at the reacting carbon is retained through the reaction, ruling out a radical pathway; (iii) the endocyclic restriction test proceeded without intramolecular amination. A Cu-catalyzed amination of Grignard reagents was realized after experiments determined the relative rates of O-acylation, transmetalation, and C–N bond formation were favorable. O-Mesitoyl N,N- dialkylhydroxylamines were found to be suitable R2N(+) synthons for the uncatalyzed amination of Grignard reagents, including unhindered vinyl Grignard reagents. iii R' R' BzO NR'2 cat Cu + R N OBz RNR'2 R2Zn SN2-like R'MgX (slow add'n) R R 2.5-15 mol % CuCl2 NOBz NR' R THF, rt 10-30 min R 58–95% yield II. Development of a 3-Exo-Dig Cyclization for the Preparation of Vinylidene Cyclopropanes The first all-carbon 3-exo-dig cyclization was developed. These cyclizations lead to vinylidene cyclopropanes with electron-withdrawing substituents, products that are not available using carbene chemistry. Both cyclic and acyclic precursors can be used with equal efficacy, although high dilution conditions were necessary to enable cyclization of the latter. The products were amenable to a number of common derivatizations, including halogenation, hydrogenation, and hydroboration. R1O O R2 R TBAF, THF R Y 2 Y 3 R1 = H, TBS X = Cl, Br, I R3 X R2 = CO2Me, CO2Et, CNY = CH2, OMe H R3 = H, Me yield 36-95% R3 R3 III. Total Synthesis of (+)-Polyanthellin A (+)-Polyanthellin A was synthesized in 15 linear steps from methallyl alcohol in 2% overall yield, with an average yield of 77% per step. This synthesis demonstrates the utility of the [3+2]-cycloaddition between cyclopropanes and aldehydes in a complex iv setting. The use of the hindered catalyst, MADNTf2, was essential to ensure a successful cyclization, and has extended the scope of the cycloaddition to include sensitive protected β-hydroxyaldehydes. Other key steps included a Cu-catalyzed cyclopropanation, ring- closing metathesis, selective alkene oxidation, and an iodoetherification. TMSO O CO Me O H 2 MADNTf2 R AcO H TMSO (10 mol %) + O OHC O O H 76% 3 equiv. H H H (+)-Polyanthellin A v ACKNOWLEDGEMENTS I would first like to acknowledge Professor Jeff Johnson for guiding my research during the five years I've been here at UNC. As I matured as a chemist, he was more than willing to let me research in my own style, but still would nudge me back on track if I started to stray away from straightforward and simple solutions. I was able to work on diverse projects throughout my tenure here that have opened me up a number of unrelated areas in synthetic chemistry. For this opportunity, I am truly grateful as I realize this is not generally true for organic students. I'm also appreciative of Jeff's ability to not pass judgment, even when I'm arguing against reason, and for humoring the bad ideas I've come up with over the years. I thank Professors Erik Alexanian, Maurice Brookhart, Joseph Templeton, and Cynthia Schauer for serving on my defense committee, and Jim Morken for serving as my committee chair for my oral examination. Thanks to past and present Johnson group members (Andrew Satterfield, Shanina Sanders, Chris Tarr, Dan Schmitt, Austin Smith, Greg Boyce, Mike Slade, Jenn Carman, and Kim Steward) for maintaining a low-key working environment that was seldom boring, and for putting up with my eccentricities of singing and being obnoxious in general. The group has always been relatively coherent even when fantasy football threatens to destroy our fine social fabric. I especially extend thanks to Pat Pohlhaus, Andrew Parsons, and Ash Berman who contributed to the projects that I've worked on at UNC. For fine conversations about chemistry and life and for being good friends, I thank Andrew Parsons, Steve Greszler, and Dave Nicewicz. Mike Barrett and Matt Haley have also been along for the ride with me. My time here (not to mention Sundays) would have been much more boring if I hadn't had met you both. Thanks for the fond memories I'll be able to take with me from Carolina. I'd like to thank my girlfriend, Miranda Welsh, for the love she has provided me for the last ten years, beginning in 11th grade AP Biology. Without you, I probably wouldn't have made it this far, and now it is your turn to finish your degree at UNC. I'm sad I won't be together for our entire academic career, but we've made it pretty far. Finally, I'd like to thank the rest of my family who have supported me over the years. My parents extended patience to me when I told them everyday or so that I wanted to live in the woods, and accepted my desire while I was out there for a little while. They were good-natured and wise enough to financially plan for their children's educations, and all four of us have benefited greatly from being able to pursue our educations without the complications money brings. My brother and his wife, Anita, have enabled me to have an immediate family in North Carolina, and my sisters, Stephanie and Kristin, have set a scholarly example since I can remember. Thanks for letting me know high school academics were a waste of time, which let me enjoy wood shop, zoology, and other such pleasures. vi TABLE OF CONTENTS LIST OF TABLES ........................................................................................................... xi LIST OF FIGURES AND SCHEMES.......................................................................... xii LIST OF ABBREVIATIONS AND SYMBOLS ......................................................... xvi CHAPTER 1 MECHANISTIC STUDIES OF A COPPER- CATALYZED ELECTROPHILIC AMINATION OF DIORGANOZINC REAGENTS BY O-BENZOYL N,N-DIALKYLHYDROXYLAMINES......................1 1.1 Introduction ...........................................................................................................1 1.2 Background............................................................................................................2 1.2.1 Mechanistic Studies of Uncatalyzed Electrophilic Aminations....................2 1.2.2 Mechanistic Studies of Copper-Catalyzed Electrophilic Aminations...........5 1.3 Results and Discussion..........................................................................................8 1.3.1 Amination with Stoichiometric Cuprates......................................................8 1.3.2 Amination of Stereodefined Organozinc Reagents.....................................10 1.3.3 Endocyclic Restriction Test ........................................................................13 1.3.4 Development of Copper-Catalyzed and Uncatalyzed Amination of Grignard Reagents with O-Acyl N,N-Dialkylhydroxylamines ..................................................15 1.3.5 Uncatalyzed Amination of Vinyl Grignard Reagents with O-Mesitoyl N,N-Diethylhydroxylamine..............................21 1.4 Conclusion...........................................................................................................22 vii 1.5 Experimental........................................................................................................23 1.6 References ...........................................................................................................57 viii CHAPTER 2 DEVELOPMENT OF A 3-EXO-DIG CYCLIZATION FOR THE PREPARATION OF VINYLIDENE CYCLOPROPANES..........................................61 2.1 Introduction .........................................................................................................61 2.2 Background..........................................................................................................61 2.2.1 3-Exo-Dig Cyclizations...............................................................................61 2.2.2 Retrosynthesis of the Cladiellin Core .........................................................65 2.2.3 Synthetic Utility of Vinylidene Cyclopropanes ..........................................68 2.3 Results and Discussion........................................................................................72 2.3.1 Attempted Synthesis via Carbene Methodology.........................................72 2.3.2 Synthesis
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