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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 film s 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 primer. 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, prim bleedthrough,m argin*,substandard 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 wiD 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 xe rographically 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. A Bell & Howell Information Company 300 North Zeeto Road Ann Arbor. Ml 46106-1346 USA 313/761-4700 800 521-0600 CHAPTER I: SYNTHESIS AND CHEMISTRY OF 1- (BENZENESULFONYL)-2-(TRIMETHYLSILYL)CYCLOPROPANE CHAPTER II: 1,1-(DILITHIO)-1-(BENZENESULFONYL)-2- (TRIMETHYLSILYL)ETHANE AS AN EFFECTIVE SYNTHETIC EQUIVALENT FOR SYMMETRICAL 1,1-DISUBSTITUTED TERMINAL OLEFINS DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Larry Yet, M.S. The Ohio State University 1995 Dissertation Committee: Approved by: Dr. Harold Shechter Dr. David J. Hart Dr. Gideon Fraenkel Advisor Department of Chemistry □MI Number: 9534096 UMI Microfora 9534096 Copyright 1995, by UMI Coapany. All rights reserved. This aicrofora edition is protected against unauthorized copying under Title 17, United States Code. UMI 300 North Zeeb Road Ann Arbor, MI 48103 To My Family and Friends ACKNOWLEDGMENTS I would like to express my sincere gratitude to Professor Harold Shechter for his complete support during the entire course of my graduate studies. His "hands off" approach to research has led me to become an independent researcher, and his outstanding classroom teaching technique has been truly inspirational. Special thanks also go to past and present members of the Shechter group who made life pleasant both in and outside the laboratory. Drs. Mark McGuiness, Naresh Mathur, and Michael Wheeler are gratefully acknowledged for their initial cooperative and intense attention given to me when I was first starting out. Thanks also are given to Sau Kee (Andy) Wong, Tony Skufca, Chris Woltermann, Kirby Kendall, and Nyenty Arrey for the friendship which sustained me through my last part of graduate school. Special mention is given to Dr. Venkat Krishnamurthy, Dr. Ron Graham and Mrs. Linda Graham for the moral support as friends who were always available during the many ups and downs over the years. Without them, life would have been a serious struggle. Finally, the Chemistry Department at The Ohio State University is gratefully acknowledged for their financial support and for the opportunity to teach at an outstanding research institution. ill VITA December 18, 1964 ...................................................................... Bom - Vancouver, British Columbia, Canada 1987 ................................................................................................. B.Sc., The University of British Columbia, Van­ couver, British Columbia, Canada 1987-1993 ....................................................................................... Teaching Assistant. The Ohio State University, Columbus, Ohio 1990 ............................................................................................... M.S., The Ohio State University, Columbus, Ohio m D OF STUDY Major Field: Chemistry Studies in Organic Chemistry iv TABLE OF CONTENTS DEDICATION.......................................................................................................................................ii ACKNOWLEDGEMENTS...................................................................................................................iii VITA......................................................................................................................................................iv LIST OF SCHEMES......................................................................................................................... vii LIST OF TABLES.............................................................................................................................. x LIST OF FIGURES............................................................................................................................xi CHAPTER PAGE I SYNTHESIS AND CHEMISTRY OF 1 -(BENZENESULFONYL)-2- (TRIMETHYLSILYL)CYCLOPROPANE Statement of Problem............................................................................. 1 Introduction ............................................................................................... 2 Results and Discussion......................................................................... 24 Summary of Results and Further Possible Investigation.....................67 Experimental Section ............................................................................ 68 II 1,1 -{DILITHIO)-1 -(BENZENESULFONYL)-2-(TRIMETHYLSILYL)ETHANE AS AN EFFECTIVE SYNTHETIC EQUIVALENT FOR SYMMETRICAL 1.1-DISUBSTITUTED TERMINAL OLEFINS Statement of Problem..........................................................................108 v Introduction ............................................................................................... 109 Previous Background.............................................................................. 116 Results and Discussion ........................ 117 Summary ................................................................................................... 124 Experimental Section .............................................................................. 124 LIST OF REFERENCES..................................................................................................................140 vt LIST OF SCHEMES Page 1 Synthetic Utility of 1-(Benzenesulfonyl)-2-(1rimethysilyl)ethane (1) ................... 1 2 Proposed Research...............................................................................................2 3 Synthetic Utility of 1-(Benzenesulfonyl)-2-(trimethysilyl)ethane (1) ...................3 4 1-(Benzenesulfonyl)-4-(trimethylsilyl)-2-butenes (14) as a 1-(1,3-Butadienyl) Anion (18) Synthon ...............................................................................................4 5 1-(Benzenesulfonyl)-4-(trimethylsilyl)-2-butenes (14) as al,l-(1,3-Butadienyl) Dianion (22) Synthon ...........................................................................................5 6 o-[(Trimethylsilyl)methyl]benzyl p-Tolyl Sulfone (23) as an o-Quinodi- methane (26) Equivalent..................................................................................... 6 7 Protodesilylation of 24 ......................................................................................... 6 B Potential Syntheses of 1-(Substituted)cyclopropenes (10) ...................... 7 9 Trapping of 1,2*Dibromocyclopropene (32) with Furan .........................8 10 Trapping of 1,2-Dibromocyclopropene (32) with Exocyclic Dienes ............... 8 1 1 Trapping of 1-Bromocyclopropene (44) with Furan and DPIBF ...................9 12 Synthesis of 1 H-Cyclopropa[b]phenanthrene (53) ...........................................10 13 Synthesis and Trapping of Spiropentadiene (58) with Furan............................11 14 Synthesis of l-(Triphenylsilyl)cyclopropene (65) ..............................................12 15 Synthesis and Trapping of H-cyclopropa[/] phenanthrene (83) with Furan 15 16 Synthesis of Benzenesulfonylcyclopropane (88) ............................................. 16 17 Synthesis of Cyclopropyl Sulfones 93 .............................................................16 18 Synthesis of Cyclopropyl Sulfones 98 .............................................................18 19 Synthesis of Cyclopropyl Sulfones 101 ........................................................... 18 20 Synthesis of Cyclopropyl Sulfones 106 ........................................................... 20 21 Synthesis of Cyclopropyl Sulfones 108 ........................................................... 21 v ii 22 Synthesis of Cyclopropyl Sulfones 124 .............................................................23 23 Synthesis of 2-Methylene-1-cyclopropyl Sulfones 126 .................................... 23 24 Retrosynthetic Syntheses of 8 ............................................................................ 25 25 Synthesis of (E)-1-(Phenylthio)-2-(trimethylsityl)ethene (127) and (E)-1-(Benzenesulfonyl)-2-(trimethylsilyl)ethene (1 2 8 ) ........................... 26 26 Preparation of (Z)-1-(p-Toluenesulfonyl)-2-(trimethylsilyl)ethene (138) ............27 27 Preparation of p-Toluenesulfonyldiazomethane (141).and Reaction of 141
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