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Borinic Acid-Catalyzed Regioselective Functionalization of Polyols

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Borinic Acid-Catalyzed Regioselective Functionalization of Polyols Borinic Acid-Catalyzed Regioselective Functionalization of Polyols by Caitlin Williamson A thesis submitted in conformity with the requirements for the degree of Master of Science Department of Chemistry University of Toronto © Copyright by Caitlin Williamson 2011 Borinic Acid-Catalyzed Regioselective Functionalization of Polyols Caitlin Williamson Master of Science Department of Chemistry University of Toronto 2011 Abstract The selective manipulation of hydroxyl groups in di- and polyols is a frequently encountered problem in organic synthesis. Such processes are often tedious and/or moderate yielding, and often necessitate multistep protection / deprotection sequences. Applying boron–diol interactions previously exploited in molecular recognition and based on methods previously developed in our research group, we have developed two classes of chemical transformations: 1. Regioselective sulfonylations of carbohydrate derivatives catalyzed by a borinic ester, providing access to the corresponding mono-tosylates in high yields; 2. Selective monoalkylations and monosulfonylations of structurally diverse 1,2- and 1,3- diol substrates. ii Acknowledgments First and foremost I would like to thank Professor Mark S. Taylor for accepting me into his research group and constantly giving me guidance. I would like to thank him for his patience whenever I felt the need to ask silly questions and for always displaying a willingness to help but at the same time trying to teach me to be more independent. I would like to thank all of the members of the Taylor group. It has been wonderful working with you and getting to know you all over the past year. None of you ever hesitated to help whenever I asked and even sometimes offering assistance before I even had to ask. You provided an amazing and friendly working environment and made my time as the University of Toronto enjoyable and worthwhile. Specifically I would like to thank Christina, Doris, and Lina for helping whenever I had questions about sugar and functionalization chemistry or experimental set-ups. I would also like to thank Corey for always being there to get supplies down for me that were too high for me to reach. Lastly, I would like to thank the entire staff of University of Toronto’s chemistry department for providing an amazing working environment. If all of you weren’t there to keep things running smoothly, completing my chemistry would have proved a lot more difficult and would not have been nearly as enjoyable. iii Table of Contents Acknowledgments.............................................................................................................................. iii Table of Contents.................................................................................................................................iv List of Abbreviations ..........................................................................................................................vi List of Tables ...................................................................................................................................... viii List of Schemes ...................................................................................................................................... x List of Figures..................................................................................................................................... xiii List of Appendices .............................................................................................................................xiv 1 Boron-Diol Interactions...............................................................................................................1 1.1 Use of Boronic Acids in Chemical Recognition of Carbohydrates ........................................1 1.2 Use of Borinic Acids in Functionalization of cis-Diols..............................................................3 2 Regioselective Sulfonylation of Polyols .................................................................................7 2.1 Introduction ...........................................................................................................................................7 2.1.1 Regioselective Sulfonylation of Polyols..................................................................................................7 2.1.2 Regioselective Sulfonylation of Carbohydrate Derivatives.........................................................13 2.2 Results and Discussion .................................................................................................................... 18 2.2.1 Regioselective Sulfonylation of Carbohydrate Derivatives.........................................................18 2.2.2 Regioselective Sulfonylation of Polyols...............................................................................................22 2.3 Conclusion............................................................................................................................................ 25 2.4 Experimental....................................................................................................................................... 25 2.4.1 General...............................................................................................................................................................25 2.4.2 Procedure and Characterization Data for TBS-Protection of Carbohydrate Derivatives 26 2.4.3 Procedure and Characterization Data for Sulfonylation of Polyols.........................................28 3 SN2 Reactions Using Carbohydrate Sulfonates.................................................................. 36 3.1 Introduction ........................................................................................................................................ 36 3.2 Results and Discussion .................................................................................................................... 37 3.3 Conclusion............................................................................................................................................ 40 4 Regioselective Deoxygenation of Carbohydrate Derivatives....................................... 41 iv 4.1 Introduction ........................................................................................................................................ 41 4.2 Results and Discussion .................................................................................................................... 43 4.3 Conclusion............................................................................................................................................ 46 4.4 Experimental....................................................................................................................................... 46 5 Regioselective Alkylation of Polyols .................................................................................... 49 5.1 Introduction ........................................................................................................................................ 49 5.2 Results and Discussion .................................................................................................................... 53 5.3 Conclusion............................................................................................................................................ 60 5.4 Experimental....................................................................................................................................... 60 6 Competition Experiments to Study Selectivity of Functionalization......................... 66 6.1 Functionalization of 1,2- and 1,3-Diols ...................................................................................... 66 6.2 Functionalization of syn and anti 1,3-Diols .............................................................................. 68 6.3 Conclusions.......................................................................................................................................... 71 6.4 Experimental....................................................................................................................................... 72 6.4.1 Procedure and Characterization Data for the Preparation of 1,3-Diols................................72 6.4.2 Procedure and Characterization Data for Competition Experiments ....................................77 7 Regioselective Benzoylation of Diols................................................................................... 81 7.1 Conclusions.......................................................................................................................................... 82 7.2 Experimental....................................................................................................................................... 82 8 Functionalization Using Epoxide Electrophiles................................................................ 84 8.1 Conclusions.......................................................................................................................................... 85 9 Conclusions................................................................................................................................... 86 Appendix A NMR Spectra ................................................................................................................ 87 v List of Abbreviations Acac Acetylacetonate AIBN Azobisisobutyronitrile
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