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University Microfilms International 300 N 8100108 Ba l o g h , D o u g l a s W a y n e THE SYNTHESIS OF SECODODECAHEDRANE AS A POTENTIAL PRECURSOR TO THE PENTAGONAL DODECAHEDRANE The Ohio State University PH.D. 1980 University Microfilms International 300 N. Zeeb Road, Ann Arbor, MI 48106 THE SYNTHESIS OF SECODODECAHEDRANE AS A POTENTIAL PRECURSOR TO THE PENTAGONAL DODECAHEDRANE DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Douglas Wayne Balo'gh, M. S. ***** The Ohio State University 1980 Reading Committee: Approved By Dr. P h ilip D. Magnus Dr. David J. Hart ________ A dviser' Dr. Leo A. Paquette Department of Chemistry ACKNOWLEDGMENTS The author gratefully acknowledges the fbllowing individuals who have contributed in varying degrees to the project: Dr. William Begley, Dr. Martin Banwell, Dr. David Bremner, and Dr. Robert Blanken­ ship. Appreciation is also expressed for the careful, concise work reported in the dissertation of the project*s initiator, Dr. Matthew J. Wyvratt, which provided a solid foundation for the work reported h ere. A special word of gratitude must be expressed to Dr. Leo A. Paquette, whose overwhelming enthusiasm and continuous interest in the project proved quite contagious. His knowledge and experience provided a lim itless wealth of ideas from which to draw. The author wishes, finally, to express appreciation to his wife and family for their encouragement, particularly to Deborah Balogh who has offered understanding and unending support throughout this work while completing her own dissertation. i i VITA May 22, 1952 ............................ Born - Painesville, Ohio 1974 ............................................ B. S., Bowling Green State University, Bowling Green, Ohio 1 9 7 4 -1 9 7 6 ....................... • • Teaching Assistant, Department of Chemistry Bowling Green State University, Bowling Green, Ohio 1976 ............................................ M.S., Bowling Green State University, Bowling Green, Ohio 1976-1977 .......................... • Teaching Associate, Department of Chemistry The Ohio State University, Columbus, Ohio 1977-1979 ............................... Research Associate, Department of Chemistry The Ohio State University, Columbus, Ohio 1979-1980 ............................... Presidential Fellow, The Ohio State Univer­ sity, Columbus, Ohio PUBLICATIONS "Synthesis and X-Ray Crystal Structure of a (C^)-Dioxatrisecododeca- hedrane," L. A. Paquette, D. Balogh, and P. Engel, Submitted for Publi­ c a tio n , ( 1980). "Unusual Photo isomerization of an "Encased" a-Diketone," D. W. Balogh, L. A. Paquette, and P. Engel, Submitted for Publication, ( 1980). "Topologically Spherical Molecules. Transannular and Other Rearrange­ ment Reactions of Bishomo Dioxatrisecododecahedranes," D. W. Balogh and L. A. Paquette, J. Org. Chem., 45 ? 3038 ( 1980). ”(Cj2)-D ioxa-C 2o-°ctaquinane, a Heterocyclic Triseco Dodecahedrane," D. Balogh, W. J. Begley, D. Bremner, M. J. Wvyratt, and L. A. Paquette, J. An. Chem. Boc.. 101, 749 (1979). "Topologically Spherical Molecules. Rearrangement Reactions of Func- tionalized £2 Symmetric Hexaquinane Systems and Synthesis of (£ 2)- Dioxa-Cao-octaquinane, a Heterocyclic Triseco Dodecahedrane," L. A. Paquette, W. J. Begley, D. Balogh, M. J. Wyvratt, and D. Bremner, J. Org. Chem., 44, 3630 (1979) • "Topologically Spherical Molecules. Synthesis of a Pair of £ 2- Symmetric Hexaquinane Dilactones and Insights into Their Chemical Reactivity. An Efficient s-Mediated 1,6-Dicarbonyl Reduction," L. A. Paquette, M. J. Wyvratt, 0. Schallner, J. L. Muthard, W. J. Begley, R. M. Blankenship, and D. Balogh, J. Org. Chem. , 44, $ 6l 6 (1979)* FIELD OF STUDY Major Field: Organic Chemistry iv TABLE OF CONTENTS Page AC KNOWLEDOMENTS.......................................................................................................... i i VITA ......................................................................................................................................i i i LIST OF FIGURES...................................................................... v i i CHAPTER I. Introduction .............................................................................................. 1 1-1 Theoretical Interest in the Pentagonal Dodeca­ hedron • •••■»*••••••••••••••• 1 1-2 General Approaches to Dodecahedrane ............................... 8 I-3 Aim of This Research and Survey of the Dis­ s e r ta tio n ......................................................................................... 12 II. Construction of the A ll-cis Fused Hexaquinane Frame­ work 13 II-l Introduction ................................................................................ 15 II-2 Review of the Domino Diels-Alder Reaction through the Bislactone (15) ................................................. 16 II-3 Avenues for Expansive Research ........................................ 24 III. The Bis Closed Lactol (£ 8) and Derived Molecules .... 27 III-l Introduction ........................................................................... 27 III-2 Oxidation of Bislactol j 8 ................................................. 28 III-3 The Bis Dihydro Pyran £4 (Reduction of Bis­ l a c t o l 38) .................................................... 29 III-3-1 Transannular Derivatives ............................... 29 III-3-2 Symmetrical Derivatives ............................... 35 III-4 Bis Epoxy Ether 63 ................................................................... 36 III-5 Bis Cyclopropyl IFElier 6 4 . ................................................. 48 IV. The Open Bismethyl Lactone (40) and Derivatives ................... 55 IV-1 Introduction ................................................................................ 55 IV-2 Lactone Ring Cleavage Reactions ........................................ 58 v TABLE OP CONTENTS Page IV-3 The Open Bis Methyl Lactol (97) ...................... 6 l IV-3-1 Transannular Derivatives ........................................ 6 l IV-3-2 Symmetrical Derivatives ............................................ 68 V. Photochemistry of Carbonyl Groups (Carbon-Carbon Bond I b r m a tio n ) ......................................................... 70 V-l Introduction ........................................................................................ 70 V-2 The Two Saturated Diesters (120 and 127) ........................... 72 V-3 An Unusual Decaquinane .................................................................. 79 VI. Trisecododecahedrane Derivatives ..................................................... 87 VI-1 Introduction .................................................................................... 87 VI-2 Methylation Products from Dissolving Metal Reduction of Dichloro Diester ^ ........................................ 88 VI-3 Photochemistry R evisited ......................................................... 93 VI-4 Trimethyl Trisecododecahedrane Derivatives .................. 95 VI-5 Dimethyl Trisecododecahedrane Derivatives .......................... 103 VI-6 Desmethyl Trisecododecahedrane Derivatives .................. 104 VII. Secododecahedrane ............................................................................................109 VII-1 Introduction ....................................................................................... 109 VTI-2 Dimethyl Secododecahedrane 1 6_ ................................................110 VII-3 Trimethyl Secododecahedrane 202 ............................... 113 VII-4 Outlook for the Future ..................................................................115 SUMMARY.......................................................................................................................... 119 EXPERIMENTAL SECTION........................................................................................... 124 PROTON NMR SPECTRA................................................................................................225 LIST OF REFERENCES................................................................................................243 vi LIST OF FIGURES Figure Page 1. Three-Dimensional Features of Dimethyldioxa- triseco Dodecahedrane 82 as Determined by X-ray A n a ly s is ................................................................................................ ^9 2. Three-Dimensional Features of a-Diketone l^J as Determined by X-ray Analysis ..................................................... 82 5- Three-Dimensional Features of Decaquinane Diol 140 as Determined by X-ray Analysis ...................................... 81j- 4. Three-Dimensional Features of Triseco Dodecahedrane IpJ as Determined by X-ray Analysis ............................... 96 v i i CHAPTER 1 INTRODUCTION 1-1 THEORETICAL INTEREST IN THE PENTAGONAL DODECAHEDRON Almost 25 centuries ago Plato mathematically defined the five uni­ form polyhedra, the Platonic solids in his Theaetetus, as the tetrahedron, 1 the cube, the octahedron, the icosahedron, and the dodecahedron. Little did he realize that the fascination he must have held for them ■would be felt as strongly by modern theoretical and synthetic chemists. The Platonic Solids: (top) tetrahedron, cube, dodecahedron; (bottom) octahedron, icosahedron. The aesthetic appeal of the Platonic solids for the chemist lies in their envisioned molecular equivalents, i. e. with an atom of a 1 2 specific element located at each of the vertices. In this respect, the inorganic chemist is
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