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INFORMATION TO USERS The most advanced technology has been used to photo graph and reproduce this manuscript from the microfilm master. UMI films the original text directly from the copy submitted. Thus, some dissertation copies are in typewriter face, while others may be from a computer printer. 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 copyrighted material had to be removed, a note will indicate the deletion. Oversize materials (e.g., maps, drawings, charts) are re produced by sectioning the original, beginning at the upper left-hand comer and continuing from left to right in equal sections with small overlaps. Each oversize page is available as one exposure on a standard 35 mm slide or as a 17" x 23" black and white photographic print for an additional charge. Photographs included in the original manuscript have been reproduced xerographically in this copy. 35 mm slides or 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. ■UMIAccessing the Worldfc Information since 1938 300 North Zeeb Road. Ann Arbor, Ml 48106-1346 USA Order Number 8804121 Synthetic approaches to structurally Interesting, spherical hydrocarbons and synthesis of monosubstituted dodecahedrane derivatives Weber, Jeffrey Charles, Ph.D. The Ohio State University, 1887 UMI 300 N. Zeeb Rd, Ann Aibor, Ml 48106 SYNTHETIC APPROACHES TO STRUCTURALLY INTERESTING, SPHERICAL HYDROCARBONS AND SYNTHESIS OF MONOSUBSTITUTED DODECAHEDRANE DERIVATIVES DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Jeffrey Charles Weber, B.A. The Ohio State University 1987 Reading Committee Approved By Dr. Anthony W. Czarnik Dr. Harold Shechter Adviser'5 F Dr. Leo A. Paquette Department of Chemistry To My Parents ii ACKNOWLEDGEMENTS I extend my sincere thanks to Professor Leo A. Paquette for providing the opportunity to complete this research. His encouragement and enthusiasm during my graduate studies are appreciated. I want to thank Anthony Schaefer for his friendship and support during our years at The Ohio State University. I owe special thanks to my family and fianc&e, Tina Kravetz, who have offered understanding and unending support throughout this work. Finally, I want to thank Kay Kampsen for her efficient and accurate preparation of this typewritten manuscript. iii VITA March 29, 1961 .............. Born - Evansville, Indiana 1983 B.A., DePauw University, Greencastle, Indiana 1983-1984 ................... Teaching Associate, Depart ment of Chemistry, The Ohio State University, Columbus, Ohio 1984-1987 ............... Research Associate, Depart ment of chemistry, The Ohio State University, Columbus, Ohio PUBLICATIONS "Intramolecular Anionic Cyclization Route to Capped [3]Peristylanes," Garratt, P.J.; Doecke, C.W.; Weber, J.C.; Paquette, L.A. J. Org. Chem. 1986, 51, 449. "The Crystal and Molecular Structure of endo.endo-2.6- Diphenacyl[4]peristylane," Engel, P.; Weber, J.C.; Paquette, L.A. Zeit. Kristallogr. 1987. "Selective Functionalization of Dodecahedrane," Weber, J.C .t Kobayashl, T.; Paquette, L.A.; presented at the 19th Central Regional Meeting of the American Chemical Society, June 25, 1987, Columbus, Ohio. FIELD OF STUDY Major Field: Organic Chemistry TABLE OF CONTENTS Page DEDICATION ....................................... ii ACKNOWLEDGEMENTS .................................. iii VITA.............................................. iv LIST OF TABLES .................................... vil LIST OF FIGURES ................................... viii LIST OF SCHEMES ................................... ix CHAPTER I. INTRODUCTION ............................. 1 II. SYNTHETIC ROUTES TO OCTAHEDRANE .......... 4 II-l. Introduction ..................... 4 II-2. Synthesis of Cyclopropyl Ether 28 . 8 II-3. Alternative Approaches to Octahedrane .................... 18 II-4. Possible Synthetic Schemes for the F u t u r e ................. 31 III. SYNTHETIC ROUTES TO DECAHEDRANE........... 33 III-l. Introduction ..................... 33 III-2. Approaches to Diketone 5 ......... 34 III-3. Review of the Initial Approaches to 2 ....................... 37 III-4. Photochemical Approaches to Capping the [4]Peristylane Framework .... 45 III-5. Synthesis of a-Diketone 99 ....... 57 III-6. Outlook for the Future ........... 63 v Table of Contents (continued) Page IV. ROUTES TO SUBSTITUTED DODECAHEDRANES ..... 67 IV-1. Introduction ................. 67 IV-2. Review of the Route to Aldehyde 1 3 5 ....................... 69 IV-3. Continuing Toward Dodecahedrane ... 75 IV-4. Dehydrogenation of Secododeca- hedrane Derivatives ............ .79 IV-5. Direct Functionalization of Dodecahedrane. Formation of Monosubstituted Derivatives .... 91 IV-6. Synthesis of Amino Derivatives .... 119 IV-7. Nuclear Magnetic Resonance Observations ................... 130 IV-8. Paving the Way to New Molecules ... 141 IV-9. Summary ..................... 147 EXPERIMENTAL SECTION ............................. 148 REFERENCES AND NOTES ................................ 211 * vi LIST OF TABLES Table Page 1. Proton NMR Chemical Shifts for Selected Dodecahedrane Derivatives (DDH-X) ......... 130 2. Carbon NMR Chemical Shifts for Selected Dodecahedrane Derivatives ................. 133 3. Substituent Effect for Selected Dodecahedrane Derivatives ............................... 134 vii LIST OF FIGURES Figure Page 1. side and Top Views of endo,endo-2#6- diphenacyl[4]peristylane (81) ............. 52 2. *H (300 MHz) and X*C (75 MHz) NMR Spectra of 163 ................................... 94 3. Carbon-Hydrogen Correlation Spectrum of 163 .. 95 4. *H (300 MHz) and 1SC (75 MHz) NMR Spectra of 175 ................................... 106 5. Carbon-Hydrogen CorrelationSpectrum of 175 .. 107 6. X-Ray Structure of Ester 175 ............... 108 7. XH (300 MHz) and 13C (75 MHz) NMR Spectra of 178 ................................... 114 8. a-Effect. Chemical Shifts (ppm) of a-Carbons, DDH-X vs. t-Bu-X .......................... 136 9. {J-Effect. Chemical Shifts (ppm) of 8-Carbons, DDH-X V S. t-BU-X ....................................................................... 136 10. f-Effect. Shifts of f-Carbons, Substituent Effects vs. oj Values .................... 138 11. 6-Effect. Shifts of 6-Carbons, Substituent Effects vs. oj Values ...................... 138 12. e-Effect. Shifts of e-Carbons, Substituent Effects vs. ag Values .................. 140 13. c*“E£fect. Shifts of c~Carbons, Substituent Effects vs. oj Values .................. 140 viii LIST OF SCHEMES Scheme Page 1 32 2 35 3 36 4 39 5 46 6 57 7 64 8 72 9 77 10 78 11 85 12 98 13 Ill 14 117 15 121 ix CHAPTER I Introduction The Paquette group has been Involved in the synthesis of a series of structurally interesting, spherical hydro carbons. This family of polycyclic saturated systems is related by having a central n-membered ring connected by alternate carbons to two (n/2)-membered rings. The sim plest of these molecules are dodecahedrane (3) and its two lower homologues £-[3s.5*]octahedrane (1) and £-[42.5®J- decahedrane (2). The successful synthesis of 3 has caused interest to become focused on the smaller polycyclic molecules. Dramatic alterations in structural topology are expected to accompany changes in n. Octahedrane and 2 decahedrane are of synthetic interest in order to define the precise nature of these geometric perturbations and to correlate the structural features with chemical react! vities. The topology of the molecules often gives rise to unexpected results in normally predictable chemical trans formations as will be exemplified in the sequel. In developing pathways to these highly symmetrical molecules, a synthetic design which takes maximum advantage of symmetry characteristics is desired. Elegant use of this concept greatly facilitated the synthesis of dodecahe drane (Chapter IV). The advantages to this strategy are obvious: first the number of steps to the target molecule is reduced by a factor of two; and second, the NMR spectra of intermediates quickly provide definition of whether the reaction has proceeded according to design. The routes to each molecule are discussed individually in the upcoming chapters. Chapter II deals with the various synthetic approaches to octahedrane from diketone 4. 0 4 Although 4 is highly symmetrical and possesses manipulative functionality, conversion to 1 has not been accomplished to date. Chapter III discusses the many approaches toward deca- hedrane from its precursor dione 5 using strategy which follows a symmetrical approach. The synthesis of 2 has 0 5 also eluded us to this time, but as with 1 much invaluable chemical knowledge of the systems has been gathered. Special interest in dodecahedrane has been shown by both synthetic and theoretical chemists. The synthesis of the hydrocarbon in 1982 did not satiate these interests because the amount of dodecahedrane available for further study was greatly restricted. Improvements in the syn thetic scheme have allowed preparation of relatively large amounts of the parent hydrocarbon for these studies to commence. Initial investigations of the system are discussed in this dissertation (Chapter IV). These advances have resulted in the synthesis of a number of functionalized dodecahedrane derivatives and set the stage for the continued study of