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INFORMATION to USERS This Manuscript Has Been Reproduced INFORMATION TO USERS This manuscript has been reproduced from the microfilm master. UMI films the text directly from the original or copy submitted. Thus, some thesis and dissertation copies are in typewriter face, while others may be from any type of computer printer. The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleedthrough, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send UMI a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. Oversize materials (e.g., maps, drawings, charts) are reproduced by sectioning the original, beginning at the upper left-hand corner and continuing from left to right in equal sections with small overlaps. Each original is also photographed in one exposure and is included in reduced form at the back of the book. Photographs included in the original manuscript have been reproduced xerographically in this copy. Higher quality 6 " x 9" black and white photographic prints are available for any photographs or illustrations appearing in this copy for an additional charge. Contact UMI directly to order. University Microfilms International A Bell & Howell Information Company 3 0 0 North Z eeb R oad. Ann Arbor. Ml 48 1 0 6 -1 3 4 6 USA 313/761-4700 800/521-0600 Order Number 9201695 Synthetic studies on dodecahedrane. Generation and reactions of its radical and anion Lagerwall, Dean Robert, Ph.D. The Ohio State University, 1991 UMI 300 N. ZeebRd. Ann Arbor, MI 48106 SYNTHETIC STUDIES ON DODECAHEDRANE. GENERATION AND REACTIONS OF ITS RADICAL AND ANION DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University by Dean Robert Lagerwall, B.S. * * * * * The Ohio State University 1991 Dissertation Committee: Approved by Professor Leo A. Paquette Professor Matthew Callstrom Professor Viresh Rawal Adviser Department of Chemistry To my parents ACKNOWLEDGEMENTS My sincere thanks are extended to Professor Leo A. Paquette for the opportunity to perforin this research in an atmosphere allowing for productivity and creativity. The enthusiasm which he demonstrated in all aspects of chemistry was both contagious and appreciated. I would like to thank the many members of the Paquette group with whom I have had contact throughout my studies at OSU. The friendship, encouragement, time and efforts which they have contributed to the group made the research environment not only fruitful but also enjoyable. I would also like to thank Professor Stuart Kulp of Moravian College for introducing me to Organic Chemistry. The fire he began in my heart has continued to grow and allowed me (with the help of many) to truely enjoy my chosen career. Finally, I thank my parents for the freedom, support and encouragement they gave me in all aspects of my life during my academic experience. VITA June 18,1963 ...................................... Born - Sacramento, CA June, 1985 ............................................. Bachelor of Science cum laude. Moravian College, Bethlehem, PA September 1985-September 1986 Graduate Teaching Associate, The Ohio State University Sepetmber 1986-June 1991 ........... Graduate Research Associate, The Ohio State University PUBLICATIONS Kiplinger, J. P.; Marshall, A. G.; Kobayashi, T.; Lagerwall, D. R.; Paquette, L. A.; Bartmess, J. E. "Measurement of the Double-Bond Strain Energy in Dodecahedrene and Adamantene by Thermochemical Bracketing of Gas-Phase Ion-Molecule Reactions." lournal of the American Chemical Society. 1989, J_LL, 6914. FIELD OF STUDY Major Field: Chemistry Studies in Organic Chemistry TABLE OF CONTENTS DEDICATION.................................................................................................... ii ACKNOWLEDGEMENTS................................................................................ iii VITA ................................................................................................................ iv LIST OF TABLES........................................................................................... viii LIST OF FIGURES........................................................................................... ix LIST OF SCHEMES............................................... x CHAPTER PAGE I. INTRODUCTION........................................................................ 1 A. Background ....................................................................... 1 B. Goal of this Research...................................................... 3 C. Organization of this T ex t.............................................. 4 II. SYNTHESIS OF DODECAHEDRANE...................................... 6 A. Synthesis of Diketodiester 8 ....................................... 6 B. Trost Sequence Applied to 1 7 .................................. 11 C. Synthesis of Dichlorodiester 2 0 ................................ 14 D. Closing the Front of the Molecule .............................. 17 E. Closing the Back of the M olecule .............................. 19 F. Improved Access to Secododecahedrane .............. 23 G. Improved Access to Dodecahedrane ....................... 26 III. DODECAHEDRYL RADICAL STUDY...................................... 33 A. Background ....................................................................... 33 1. Targeting Radical Precursors ......................... 33 2. Derivatization Methods Available ................ 37 B. Radical Precursors ......................................................... 39 1. Iodododecahedrane ........................................... 39 2. (Phenylseleno)dodecahedrane 42 v C. Dodecahedryl Radical Generation .............................. 46 1. Reaction Design .................................................... 46 2. Reaction With Acrylonitrile ............................ 47 3. Trapping of 56 With Acrylates ..................... 50 4. Attem pted Trapping of 56 With 6 land 62 .................................................. 56 5. Trapping With 2-Cyclopentenone ................ 58 6 . Addition-Elimination Methodology .............. 60 D. Conclusion ......................................................................... 69 References ............................................................................... 72 IV. DODECAHEDRYL ANION STUDY......................................... 77 A. Background ...................................................................... 77 B. Radical Anion Methodology ......................................... 78 1. Alternate Anion Precursor .............................. 81 2. Reaction Design .................................................... 83 C. Transmetallation Methodology .................................. 86 1. Reaction Design .................................................... 86 2. Single Electron Transfer Exploration 94 D. Conclusion ......................................................................... 96 References ............................................................................... 98 V. EXTENSIONS TO DODECAHEDRYL CATION CHEMISTRY 102 A. Background ...................................................................... 102 B. Utilization of Zinc Iodide ............................................. 103 C. Dodecahedryl Alcohol: Improved Synthesis 107 D. l,4-Di(dodecahedryl)benzene .................................... 108 E. Conclusion ........................................................................... 112 References ............................................................................... 114 VI. DODECAHEDRENE................................................................... 116 A. Introduction .................................................................... 116 B. Measurement of the Double-Bond Strain Energy of Dodecahedrene by Thermochemical Bracketing of Gas-Phase Ion-Molecule Reactions ...................................................................... 117 1. Background ................................................. 117 vi 2. T heory .................................................................... 118 3. R esults .................................................................... 119 C. Dodecahedrene: Laboratory Synthesis and Trapping .................................................................. 127 1. Background ........................................................... 127 2. R esults .................................................................... 127 D. S u m m ary ........................................................................... 132 References ............................................................................... 133 VII ATTEMPTED REGIOSPECIFIC DISUBSTITUTION 135 A. Background ...................................................................... 135 B. R esults ............................................................................... 139 C. Conclusion ........................................................................... 144 References ............................................................................... 146 EXPERIMENTAL SECTION........................................................................... 148 APPENDIX A.................................................................................................... 165 APPENDIX B...................................................................................................
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