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The Synthesis and Conformational Analysis of 13- and 14-Membered Macro-Cyclic Ethers

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The Synthesis and Conformational Analysis of 13- and 14-Membered Macro-Cyclic Ethers The Synthesis and Conformational Analysis of 13- and 14-Membered Macro-cyclic Ethers by DEAN SUTHERLAND CLYNE B.Sc, The University of Lethbridge, 1990 A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY in THE FACULTY OF GRADUATE STUDIES (Department of Chemistry) We accept this thesis as conforming to the required standard THE UNIVERSITY OF BRITISH COLUMBIA January, 1998 © Dean S. Clyne, 1998 In presenting this thesis in partial fulfilment of the requirements for an advanced degree at the University of British Columbia, I agree that the Library shall make it freely available for reference and study. I further agree that permission for extensive copying of this thesis for scholarly purposes may be granted by the head of my department or by his or her representatives. It is understood that copying or publication of this thesis for financial gain shall not be allowed without my written permission. Department The University of British Columbia Vancouver, Canada DE-6 (2/88) ii ABSTRACT As part of an ongoing study of the chemistry of macrocyclic compounds in our laboratory, the 14-membered macrocyclic ethers 90, 92, 103, 104, 116, 119, 137, and 154, and the 13-membered macrocyclic ethers 168, 171, 179, 180, 190, and 193 with substituents both close to and remote from the oxygen atom were synthesized. The strategy for the preparation of these macrocyclic ethers involved either the Baeyer- Villiger ring expansion of a cyclic ketone, or the macrolactonization of a long chain hydroxy acid to give a lactone. Ultimately, the ether oxygen of the lactone would become the oxygen of the macrocyclic ether. The lactone was often used to introduce substituents in the vicinity of the ether oxygen. Once this purpose was served, the carbonyl of the lactone was removed either via a conversion to an intermediate thionolactone obtained by reaction with Lawesson's reagent, or reduced directly via a boron trifluoride etherate mediated sodium borohydride reaction. The diastereomeric 14-membered ethers 103 and 104, and the 13-membered ethers 179 and 180 were prepared under both radical reduction and hydrogenation conditions, and the stereoselectivities of these methods were compared. In general, the stereoselectivities were low (<18% d. e.). The relative configurations of 103, 104, 179, and 180 were determined through chiral GC analysis. The unsaturated 14-membered ethers 157, 158, 163, and 164 were prepared via the ruthenium catalyzed metathesis of an acyclic diene ether. The configuration of the double bond in these unsaturated ethers was determined with1 H homonuclear decoupling NMR experiments. The isomerization of the carbon-carbon double bond using phenyl disulfide under photolysis conditions was studied. The product ratios of the metathesis cyclization and the isomerization reactions were compared to values obtained from molecular mechanics calculations. The conformation of the 13- and 14-membered ethers was analyzed using both NMR spectroscopy and molecular mechanics calculations. The diamond lattice Ill conformations were good starting points in the analysis of the 14-membered rings but were not suited to the 13-membered rings. The [13333] conformation was found to be a good model for the analysis of the odd-sized 13-membered rings. Additional H-DNM1 R experiments were performed at low temperatures where the conformational interconversion rates of the macrocyclic ethers were slowed. The DNMR spectra were interpreted using predicted A8 values from both anisotropy and van der Waals steric compression effects. The results from the analysis of the DNMR spectra and the molecular mechanics calculations were compared. The calculations often gave one or two preferred low energy conformations with a regular geometry. The alkyl substituents were found to complicate the conformations of some of the macrocyclic ethers studied. The transition state energies of the individual macrocyclic ethers were determined from the DNMR spectra to be approximately 8-10 kcal/mol in the case of the 14-membered ethers and 6-8 kcal/mol in the case of the 13-membered ethers. The 14-membered ether values were compared to computer calculated values obtained using a dihedral drive method. The calculated values were in general higher and in the range of 10-15 kcal/mol. V TABLE OF CONTENTS Abstract ii Table of Contents v List of Schemes viii List of Figures x List of Tables xiii Abbreviations xvi Acknowledgments xix 1 Introduction 1 1.1.1 Synthesis of Macrocyclic Ethers by Intramolecular O-Alkylation 3 1.1.2 Synthesis of Macrocyclic Ethers by Olefin Metathesis 4 1.1.3 Synthesis of Macrocyclic Ethers from Macrocyclic Lactones 8 1.2.1 Conformational Analysis 20 1.2.2 Nuclear Magnetic Resonance in Conformational Analysis 20 1.2.3 Conformational Analysis of 6-Membered Rings 27 1.2.4 Conformational Analysis of Medium and Large Rings 30 1.2.5 Conformational Analysis of 14-Membered Rings 33 1.2.6 Conformational Analysis of 13-Membered Rings 38 1.2.7 Transition State Theory in Large Rings 40 2 14-Membered Macrocyclic Ethers 45 2.0.1 Synthesis of 14-Membered Macrocyclic Ethers 46 2.0.2 Conformational Analysis of 14-Membered Macrocyclic Ethers 48 2.1.1 Synthesis of Oxacyclotetradecane (90) and 2-Methyloxacyclotetra- decane (92) 50 2.1.2 Conformational Analysis of Oxacyclotetradecane (90) 52 2.1.3 Conformational Analysis of 2-Methyloxacyclotetradecane (92) 64 2.2.1 Synthesis of 2,14-Dimethyloxacyclotetradecanes (103) and (104) 73 vi 2.2.2 Conformational Analysis of (2R*, 14R*)-2,14-Dimethyloxacyclotetra- decane (103) 82 2.2.3 Conformational Analysis of (2S*, 14R*)-2,14-Dimethyloxacyclotetra- decane(104) 91 2.3.1 Synthesis of 2,2-Dimethyloxacyclotetradecane (116) 100 2.3.2 Conformational Analysis of 2,2-Dimethyloxacyclotetradecane (116) 108 2.4.1 Synthesis of 3,3-Dimethyloxacyclotetradecane (119) 117 2.4.2 Conformational Analysis of 3,3-Dimethyloxacyclotetradecane (119) 118 2.5.1 Synthesis of 6,6-Dimethyloxacyclotetradecane (137) 128 2.5.2 Conformational Analysis of 6,6-Dimethyloxacyclotetradecane (137) 136 2.6.1 Synthesis of 8,8-Dimethyloxacyclotetradecane (154) 146 2.6.2 Conformational Analysis of 8,8-Dimethyloxacyclotetradecane (154) 154 2.7.1 Conclusion 160 3 14-Membered Macrocyclic Unsaturated Ethers 166 3.1.1 Synthesis of (Z/E)-Oxacyclotetradec-5-enes (157) and (158) 167 3.1.2 Cis-Trans Isomerization of (Z/E)-Oxacyclotetradec-5-ene169 (157) and (158) 169 3.2.1 Synthesis of (Z/E)-14-Methyloxacyclotetradec-5-enes (163) and (164) 172 3.2.2 Cis-Trans Isomerization of (Z/E)-14-Methyloxacyclotetradec-5-enes (163) and (164) 176 3.3.1 Conclusion 178 4 13-Membered Macrocyclic Ethers 180 4.0.1 Synthesis of 13-Membered Macrocyclic Ethers 180 4.0.2 Conformational Analysis of 13-Membered Macrocyclic Ethers 181 4.1.1 Synthesis of Oxacyclotridecane (168) and 2-Methyloxacyclotri- decane(171) 185 4.1.2 Conformational Analysis of Oxacyclotridecane (168) 187 4.1.3 Conformational Analysis of 2-Methyloxacyclotridecane (171) 193 4.2.1 Synthesis of 2,13-Dimethyloxacyclotridecanes (179) and (180) 199 4.2.2 Conformational Analysis of 2,13-Dimethyloxacyclotridecane (179) .. 205 4.2.3 Conformational Analysis of 2,13-Dimethyloxacyclotridecane (180) .. 210 4.3.1 Synthesis of 2,2-Dimethyloxacyclotridecane (190) 216 4.3.2 Conformational Analysis of 2,2-Dimethyloxacyclotridecane (190) .... 220 4.4.1 Synthesis of 3,3-Dimethyloxacyclotridecane (193) 227 4.4.2 Conformational Analysis of 3,3-Dimethyloxacyclotridecane (193) .... 228 4.5.1 Conclusion 236 4.6.1 General Conclusion 236 5 Experimental 239 5.1.1 General 239 5.1.2 Conformational Analysis Methods 242 5.1.3 Chemical Methods 242 References 336 Spectral Appendix 345 LIST OF SCHEMES Scheme 1. Synthesis of Laurenan (37) 14 Scheme 2. Conversion of Thionocaprolactone (61) into an Oxacyclo- heptane63 19 Scheme 3. Synthesis of the BCD ring Fragment 67 of Brevetoxin A (1) 19 Scheme 4. Synthetic Strategy for the Preparation of Macrocyclic Ethers 47 Scheme 5. Synthesis of Oxacyclotetradecane (90) and 2-Methyloxacyclotetra- decane (92) 51 Scheme 6. Retrosynthetic Analysis of 2,14-Dimethyloxacyclotetradecanes (103) and (104) 74 Scheme 7. Synthesis of 2-Methylcyclotridecanone (97) via 1-Dibromomethyl- cyclododecanol (94) 75 Scheme 8. Synthesis of 2,14-Dimethyloxacyclotetradecanes (103) and (104) via Thionolactone 101 77 Scheme 9. Synthesis of 2,14-Dimethyloxacyclotetradecanes (103) and (104) via Enol Ether 100 78 Scheme 10. Retrosynthetic Analysis of 2,2-Dimethyloxacyclotetradecane (116) ... 101 Scheme 11. Synthesis of 2,2-Dimethylcyclotridecanone (106) 102 Scheme 12. Retrosynthetic Analysis of 13-Methyl-13-tetradecanolide (114) 104 Scheme 13. Synthesis of 13-Methyl-13-tetradecanolide (114) 105 Scheme 14. Synthesis of 3,3-Dimethyloxacyclotetradecane (119) 118 Scheme 15. Retrosynthetic Analysis of 6,6-Dimethyloxacyclotetradecane (137) ... 129 Scheme 16. Synthesis of 8-Bromooctanal ethylene acetal (123) 130 Scheme 17. Synthesis of Bisalkylated Dithiane 127 131 Scheme 18. Synthesis of 9-Methylene-13-hydroxytridecanoic acid (131) 133 Scheme 19. Synthesis of 6,6-Dimethyloxacyclotetradecane (137) 135 Scheme 20. Retrosynthetic Analysis of 8,8-Dimethyloxacyclotetradecane (154) ... 147 Scheme 21. Synthesis of Alkylating Agents 141 and 142 148 Scheme 22. Synthesis of 7-Methylene-13-hydroxytridecanoic acid (149) 151 Scheme 23. Synthesis of 8,8-Dimethyloxacyclotetradecane (154) 153 Scheme 24. Synthesis of Oxacyclotetradec-5-enes (163) and (164) 168 ix Scheme 25. Retrosynthetic Analysis of 14-Methyloxacyclotetradec-5-enes (163) and (164) 172 Scheme 26. Synthesis of 14-Methyloxacyclotetradec-5-enes (163) and (164) 174 Scheme 27. Synthesis of Oxacyclotridecane (168) and 2-Methyloxacyclotri- decane(171) 186 Scheme 28. Synthesis of 2-Methyloxacyclotridecane (171) via Hydrogenation 187 Scheme 29. Retrosynthetic Analysis of 2,13-Dimethyloxacyclotridecanes (179) and (180) 199 Scheme 30. Synthesis of 2,13-Dimethyloxacyclotridecanes (179) and (180) via Radical Reduction 201 Scheme 31. Synthesis of 2,13-Dimethyloxacyclotridecanes (179) and (180) via Hydrogenation 202 Scheme 32.
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