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Mechanistic Insights Towards New Reactions and Materials MECHANISTIC INSIGHTS TOWARDS NEW REACTIONS AND MATERIALS A DISSERTATION SUBMITTED TO THE DEPARTMENT OF CHEMISTRY AND THE COMMITTEE ON GRADUATE STUDIES OF STANFORD UNIVERSITY IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY Matthew Karl Kiesewetter October 2010 © 2011 by Matthew Karl Kiesewetter. All Rights Reserved. Re-distributed by Stanford University under license with the author. This work is licensed under a Creative Commons Attribution- Noncommercial 3.0 United States License. http://creativecommons.org/licenses/by-nc/3.0/us/ This dissertation is online at: http://purl.stanford.edu/dk657vx4442 ii I certify that I have read this dissertation and that, in my opinion, it is fully adequate in scope and quality as a dissertation for the degree of Doctor of Philosophy. Robert Waymouth, Primary Adviser I certify that I have read this dissertation and that, in my opinion, it is fully adequate in scope and quality as a dissertation for the degree of Doctor of Philosophy. Eric Kool I certify that I have read this dissertation and that, in my opinion, it is fully adequate in scope and quality as a dissertation for the degree of Doctor of Philosophy. Barry Trost Approved for the Stanford University Committee on Graduate Studies. Patricia J. Gumport, Vice Provost Graduate Education This signature page was generated electronically upon submission of this dissertation in electronic format. An original signed hard copy of the signature page is on file in University Archives. iii ABSTRACT Catalysis is the enabling science of polymer synthesis, and new catalytic mechanisms yield new materials. The development of organocatalysts for polymer synthesis has, particularly in the last decade, spawned an impressive array of new catalysts, processes and mechanistic insights. While the focus of most recent research in organocatalysis has concentrated on enantioselective synthesis of small molecules, organocatalysis offers a number of opportunities in polymer synthesis and was among the earliest methods of catalyzing the synthesis of polyesters. The enthalpy of ring opening of cyclic esters or carbonates drives the majority of organocatalytic polymerization reactions catalyzed by a still-evolving array of organocatalysts. Organocatalysts are thought to effect polymerization of cyclic esters by several mechanisms. Some proceed via a monomer activated mechanism whereby the catalyst activates the cyclic ester towards transesterification to the polymer chain. Others operate by an alcohol activation mechanism where the alcoholic end group of the growing polymer chain is activated to induce transesterification. Some are thought to be operative by a combination of these mechanisms. The unique reactivity offered by organocatalysts has provided access to precisely controlled macromolecular architectures and well-defined (co)polymers including a wide array of functionality. The notion that rate must be sacrificed to implement organocatalysts is fading with the discovery of transesterification organocatalysts that rival in reaction rate even the most active metal-containing catalysts. Cyclopentadienyl ruthenium complexes with quinaldic acid-type ligands are robust allylation catalysts in alcoholic solvents, but they are sensitive to dissolved oxygen, requiring reactions to be conducted in an inert atmosphere. Moving from alcoholic to neat aqueous solvents decreases the rate of deallylation but allows the reaction to be conducted in air without loss of catalyst activity over the course of the reaction. These complexes are also effective for the formation of allyl ethers, allowing the synthesis of poly(2,5-dihydrofuran) from the condensation polymerization of 2- cis-butene-1,4-diol. This material was previously deemed inaccessible via traditional polycondensation catalysts. iv PREFACE Chapter 1 is a review of organocatalysis as it pertains to the polymer synthesis with a particular emphasis on ring opening polymerization. It is intended to give the reader a background in concepts pertaining to metal-free polymer synthesis and a comparison between those methods. This article was published as a Perspective in Macromolecules and was co-authored by Eun Ji Shin, Dr. James L. Hedrick and Professor Robert M. Waymouth. Chapter 2 pertains to the peculiar reactivity of a single N-heterocyclic carbene and the specialized polymer architectures that can be generated from this catalyst and specialized initiators. The initial work on this system was performed by Andrew Mason, Prof. Philippe Dubois and Dr. Olivier Coulembier. The synthesis of the macromolecular initiators, initial characterization (MALDI, and Mw versus time plots) was performed by Andrew Mason and Dr. Olivier Coulembier. This chapter is largely reproduced from an Angewandte Chemie communication. Chapter 3 concerns the marked increase in reactivity of 1,5,7- triazabicyclo[4.4.0]dec-5-ene (TBD) relative to another guanidine catalyst 1,4,6- triazabicyclo[3.3.0]oct-4-ene (TBO). The reactivity of the two species in amidation and polymerization reactions is explored and a kinetic analysis is performed. The synthesis of TBO and the polymerization reactions with this catalyst were performed by Dr. Marc Scholten. The kinetic analyses and reagent screening with TBD were formed by undergraduate researchers Ryan Weber and Nicole Kirn, but the experimental designs were my own. This chapter is largely reproduced from a J. Org. Chem. publication. Chapter 4 outlines the synthesis of the first in a new class of molecular transporters made by the ring-opening polymerization of functionalized carbonates. The initial syntheses of 4.4, 4.3 and 4.6a-c were performed by Dr. Fredrik Nederberg. I devised the synthesis of 4.4b and 4.6d-e and synthesized all of 4.6 used in the biological assays for publication. I performed all oligomerization reactions for materials used in the final J. Am. Chem. Soc. publication. The experiments and syntheses pertaining to quinine were performed by undergraduate researcher Justin v Edward (with the exception of the MTC-quinine synthesis which I performed), but the experimental designs were my own. The syntheses of 4.8, 4.11, and 4.12 were my own design and execution. All other syntheses were performed by Christina Cooley or Brian Trantow as were all biological experiments. The text of the original communication was a collaborative effort between all co-authors (see the printed communication: J. Am. Chem. Soc. 2009, 131, 16401). Chapter 5 details the kinetic analysis of a deprotection of allyl alcohol reaction by a cyclopentadienyl ruthenium kynurenic acid allylation catalyst that is stable in air and water. A solid supported version of the catalyst is also discussed. All the work in this chapter was performed by me. At the time of printing, this chapter was submitted to Organometallics for publication. Chapter 6 reports the synthesis of a heretofore unobtainable polymer from cis- 2-butene-1,4-diol formed with a Ru allylation catalyst. All of the experiments described in this chapter were my own design although some experiments (small molecule allylation reactions, lactide polymerizations and a repeated catalyst synthesis) were performed by Justin Edward. At the time of printing, this chapter was in final preparation for submission to J. Am. Chem. Soc. Chapter 7 outlines out attempts to characterize the anion radicals of several N- heterocyclic carbenes. The work in the chapter was performed by me. vi ACKNOWLEDGEMENTS It is always the solvent. I have many people to whom I owe a great deal of credit. To not miss a single person would exceed the confines a reasonable acknowledgements section. First, I would like to thank my committee for all the hard work they have done for me: Prof. Wender (my de facto co-advisor on Chapters 4 and 5) and Prof. Contag, and especially Profs. Kool and Trost for serving on my committee for 4 years. I would like to express my gratitude to Prof. Robert (Bob) Waymouth. His enthusiasm for ‘cool’ science and his desire to always take a project to the next level are unbelievably motivating. His sense of humor is a source of joy in the lab and has always driven me to come up with some new ‘cute’ comment for Bob. Further, Bob possesses the best quality in an advisor: you can always hear him coming. As I construct the section on my wonderful lab mates, I come to realize the trait that I most cherish in a person is their ability to take a joke. I will leave to others the commentary about what that says about me. However, the quality of coworkers that I have shared lab space with over the years far defies the statistics of random coworker generators. Dr. Nahrain Kamber became a good friend in the couple years that we were bench neighbors, and her influence has outlasted her physical presence in my life. Dr. David Pearson and I have the ability to find humor and trouble in far more obscure places than the average duo. I will never forget tremendous fun we have had or the Variac that paid the ultimate price. Eun Ji (Eunj) Shin is one of the kindest people that I have ever met, and consequently one of the people that I tease the least. Once I finally got her to speak, we quickly became good friends. I will miss our therapy sessions. It has been fun watching people grow as chemists over the years. I would like to thank Hayley(meister) Brown for knowing all the rules. I trust that Kristen Brownell’s relationship with gravity will improve even more with time, and Jeff Simon (the youngest Waymite) has the drive to succeed in graduate school. Even though they do not need it, I wish these people the best of luck at getting what they want in life. vii Over my years at Stanford, I have had the opportunity to work with several undergraduate researchers from whom I may have learned more than I taught. Ryan Weber was (and continues to be) a gifted scientist, and I was forced to learn so much just to stay a couple of paces ahead of him.
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