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University’ Micronlrns Internatkxvil 300 N ZeebRoad Ann Arbor, Ml 48106 8305415 Yan, Tu-Hsin SILICON-MEDIATED PREPARATION OF FUNCTIONALIZED SPIROCYCLES. SYNTHESIS OF SPIROVETIVANE SESQUITERPENES The Ohio Stale University PH.D. 1982 University Microfilms International300 N Zeeb Road. Ann Arbor. Ml 48106 SILICON-MEDIATED PREPARATION OF FUNCTIONALIZED SPIROCYCLES. SYNTHESIS OF SPIROVETIVANE SESQUITERPENES DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Tu-Hsin Yan, M.S. The Ohio State University 1982 Reading Committee: Approved By Dr. Robert J. Ouellette Dr. David J. Hart A'dvi st Dr. Leo A. Paquette Department of Chemistry To my Parents i i ACKNOWLEDGMENTS I gratefully acknowledge the patience and constant encouragement of Professor L. A. Paquette which made this work possible. I would also like to thank the members of the Paquette research group, past and present, whose comments and friendship made this period of my life a very enjoyable one. Thanks are also extended to Mr. Dick Weisenberger and various members of the Paquette group for obtaining spectra. I would also like to thank Mr. Hsi-Pai Hsiu for his intelligent, timely discussions during the course of this work. Mostly I would like to thank my family and my fiancee for their constant love, support, and encouragement. VITA May 2, 1950 .... Born - Taiwan, Republic of China 1972 ........................... B.A., Chung Hsing University, Taichung, Taiwan 1976 ........................... M.S., Taiwan University, Taipei, Taiwan 1978-1980 .................. Teaching Associate, Department of Chemistry, The Ohio State University, Columbus, Ohio 1980-1982 .................. Research Associate, Department of Chemistry, The Ohio State University, Columbus, Ohio PUBLICATIONS "Silicon in Organic Synthesis. 14. Five Ring Annulation Processes Based upon Thermal Rearrangement of (1-Trimethyl silylcyclopropyl )ethy- lenes," L. A. Paquette, G. J. Wells, K. A. Horn, and T. H. Yan, Tetrahedron Lett., 263 (1982). "Silicon in Organic Synthesis. 16. A Short Synthesis of (—)- -Vetispirene," T. H. Yan and L. A. Paquette, Tetrahedron Lett., 322/ (1982). ■'Silicon in Organic Synthesis. 17. Cyclopentannulation by Thermolysis of (1-Trimethylsilylcyclopropyl)ethylenes. The 1-Trimethylsilylcyclopropyl Anion," L. A. Paquette, G. J. Wells, K. A. Horn, and T. H. Yah, submitted for publication (1982). FIELD OF STUDY Organic Chemistry iv TABLE OF CONTENTS Page DEDICATION........................................................................................................................... ii ACKNOWLEDGMENTS .............................................................................................................. iii VITA........................................................................................................................................ iv LIST OF TABLES.................................................................................................................. vii LIST OF FIGURES...................................................................................................................viii INTRODUCTION ...................................................................................................................... 1 Chapter 1. A STUDY OF THE USE OF E-TRIMETHYL(3-HALO- 1-METHYL-l-PROPENYL)SILANE AND 2-TRIMETHYLSILYLPROPENYL BROMIDE .............................................................. 2 1.1 Introduction ........................................................................................... 2 1.2 Synthetic Approach .............................................................................. 4 1.3 Conclusions ................................................................................................ 12 2. SYNTHESIS AND THERMAL REARRANGEMENT OF (l-TRIMETHYLSILYLCYCLOPROPYL)ETHYLENES ................................................. 14 2.1 Introduction ............................................................................................ 14 2.2 Synthesis of (1-Trimethylsilylcyclo­ propyl )ethyl e n e s .................................................................................... 17 2.3 Thermal Isomerization Studies ........................................................... 49 2.4 Conclusions ................................................................................................ 68 3. SPIRO 4,5 DECANE SESQUITERPENES AND A SHORT SYNTHESIS OF ( t ) -OC-VETISPI RENE.................................................................. 71 3.1 Introduction ............................................................................................ 71 3.2 Five-membered Spiroannelation Methodology ................................................................................................. 73 3.3 Synthesis ..................................................................................................... 95 3.4 Conclusions ................................................................................................ 116 v Page 4. A CONVENIENT PREPARATION OF A SYNTHETIC PRECURSOR OF SPIROVETIVANE-TYPE SESQUITERPENOIDS. 2-CYAN0-6,1Oc- DIMETHYL-tSrC1)-SPIR0C4,5}DECA-1,6-DI ENE..........................................................118 4.1 Introduction ............................................................................................................118 4.2 Synthesis ....................................................................................................................120 4.3 Conclusions ................................................................................................................131 EXPERIMENTAL ........................................................................................................................... 133 REFERENCES....................................................................................................................................184 vi LIST OF TABLES Table Page 1-1 Reactions of 2-Cyclohexenone with 1 0 .................................................... 9 1-2 Photooxygenation of ^ 9 , .................................................................................. 11 2-1 Attempted Cyclopropanation Conditions of ^ 3 7 .................................. 21 2-2 Attempted Aldol Condensation Conditions of 94, with cyclohexanone ................................................................................... 46 2-3 Isomerization of A1kylcyclopropanes .................................................... 50 2-4 Isomerization of Vinylcyclopropanes .................................................... 51 3-1 Attempted Friedel-Crafts Acylation Conditions of 208 and 2 Q 7 ........................................................................... 103 3-2 Attempted Electrophi1ic Substitution Conditions of 2jQ8 and 2 0 ? ........................................................................... 104 3-3 Attempted Transformation (Epoxysi 1ane-- Ketone or Ketal) Conditions of ^ £ 8 ......................................................... 106 3-4 Attempted Coupling Reaction Conditions of 328 with Isopropenylcuprate ...................................................................... 107 4-1 Attempted Desiliconation-Acylation Conditions of 123 4-2 Attempted Desiliconation-Alkylation Conditions of 20§ with Acetaldehyde ............................................ 124 4-3 Reactions of 2Q6,with Cyanogen R eagents ........................................... 126 vi i LIST OF FIGURES Page Retrosynthetic Analysis of 6 and 7, . 4