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Acrobat Distiller, Job 5 1-Bromo-1-lithioethene as a building block for organic synthesis A dissertation submitted to Kent State University in partial fulfillment of the requirements for the degree of Doctor of Philosophy by Yehor Novikov November 2005 Dissertation written by Yehor Novikov M.S., Lviv Polytechnic Institute, Ukraine, 1991 Ph.D., Kent State University, 2005 Approved by Dr. Paul Sampson, Chair, Doctoral Dissertation Committee Dr. Alex Seed, Members, Doctoral Dissertation Committee Dr. Michael Tubergen Dr. John Stalvey Dr. Md. Kazim Khan Accepted by Dr. Roger Gregory, Chair, Department of Chemistry Dr. John Stalvey, Dean, College of Arts and Sciences ii TABLE OF CONTENTS LIST OF SCHEMES.......................................................................................................VI LIST OF FIGURES ........................................................................................................XI LIST OF TABLES ...................................................................................................... XIII LIST OF ABBREVIATIONS AND DEFINITIONS ................................................XVI CHAPTER 1. INTRODUCTION .................................................................................... 1 1.1. Why 1-bromo-1-lithioethene? .................................................................................. 1 1.2. Published precedents of 1-halo-1-lithioalkene syntheses......................................... 4 1.3. Preparation and synthetic applications of α-bromoallylic alcohols 8 resulting from electrophilic trapping of 1-bromo-1-lithioethene (7) with carbonyl compounds .......... 13 CHAPTER 2. SYNTHESIS AND STRUCTURE OF 1-BROMO-1-LITHIOETENE (7) ...................................................................................................................................... 22 2.1. Cryogenic reactor design ........................................................................................ 22 2.2. Optimization of the preparation of 1-bromo-1-lithioethene (7) ............................. 34 2.3. Computational evaluation of deprotonation versus halogen-metal exchange reactions of bromoethene............................................................................................... 37 2.4. Possible solid state structure of 1-bromo-1-lithioethene (7) .................................. 41 CHAPTER 3. ELECTROPHILIC TRAPPING OF 1-BROMO-1-LITHIOETHENE ........................................................................................................................................... 49 3.1. Reactions of 1-bromo-1-lithioethene (7) with simple carbonyl compounds.......... 49 3.2. Reactions of 1-bromo-1-lithioethene (7) with protected α-hydroxy ketones......... 51 iii 3.3. Application of 1-bromo-1-lithioethene (7) toward the synthesis of a Physalin fragment.........................................................................................................................59 3.4. Reaction of 1-bromo-1-lithioethene (7) with highly electrophilic aldehydes ........ 64 3.5. Reaction of 1-bromo-1-lithioethene (7) with acetyltrimethylsilane ....................... 70 3.6. Electrophilic trapping of 1-bromo-1-lithioethene (7) with non-carbonyl electrophiles...................................................................................................................71 3.6.1. Trapping 7 with silicon-based electrophiles .................................................... 71 3.6.2. Trapping 7 with tributylchlorostannane and iodine ......................................... 77 CHAPTER 4. IRELAND-CLAISEN REARRANGEMENT OF α-BROMOALLYLIC ESTERS..................................................................................... 80 4.1. Introduction ............................................................................................................ 80 4.2. Ireland-Claisen rearrangement of simple α-bromoallylic propionates................... 85 4.3. Synthesis of 6-hydroxy-4-bromopent-4-enoic acids .............................................. 90 4.4. Synthesis of 3-bromo-3,5-pentadienoic acids ........................................................ 94 4.5. Attempted partial synthesis of VM55599............................................................. 104 CHAPTER 5. CONCLUSIONS................................................................................... 113 CHAPTER 6. EXPERIMENTAL DETAILS.............................................................115 6.1. General.................................................................................................................. 115 6.2. Low temperature reactor design ........................................................................... 116 6.2.1. Modes for operation of the reactor................................................................. 118 6.2.2. Notes on setting up the reactor....................................................................... 118 6.3. Experimental details for Chapter 3....................................................................... 119 iv 6.4. Experimental details for Chapter 4....................................................................... 156 CHAPTER 7. REFERENCES ..................................................................................... 186 v LIST OF SCHEMES Scheme 1. Potential synthetic utility of 1-halo-1-lithioalkanes .......................................... 3 Scheme 2. Epoxide formation during the reaction of 1-bromo-1-lithioethane with an aldehyde ...................................................................................................................... 3 Scheme 3. Generation of 1-chloro-1-lithioethene (4) ........................................................ 5 Scheme 4. An example of Fritsch-Buttenberg-Wiechell rearrangement ............................ 5 Scheme 5. Anti- diastereoselectivity of 1-bromo-1-alkenyllithium addition to MEM- protected lactaldehyde................................................................................................. 6 Scheme 6. Some selective reactions of 1,1-disubstituted versus 1,1,2-trisubstituted double bonds ...........................................................................................................................7 Scheme 7. Reported preparation and trapping of 1-iodo-1-lithioethene............................. 8 Scheme 8. Generation and trapping of 4 in the presence of a zirconium electrophile........ 8 Scheme 9. Possible reaction pathways for reaction of 4 with zirconocenes ....................... 9 Scheme 10. The single reported case of 1-bromo-1-lithioethene formation and trapping with Me3SiCl............................................................................................................. 10 Scheme 11. Potential synthesis of α-bromoallylic alcohols 8 .......................................... 12 Scheme 12. Examples of Pd(0) catalyzed reactions of α-bromoallylic alcohols.............. 13 Scheme 13. CuCl-catalyzed Stille coupling of an alkenylstannane derived from an α- bromoallylic alcohol.................................................................................................. 14 Scheme 14. Substitution of the bromine atom in 8 for a methyl group ............................ 14 Scheme 15. Application of 8 in Calcitriol core synthesis ................................................. 15 vi Scheme 16. Synthetic transformations of 8 with retention of the bromine substituent .... 15 Scheme 17. Usage of 8 in the synthesis of Kallolide B skeleton...................................... 16 Scheme 18. Indole synthesis via α-bromoallylic alcohols (8) .......................................... 17 Scheme 19. An example of diastereoselective tetrahydropyran synthesis from 8............ 17 Scheme 20. Synthesis of α-bromoallylic alcohols via HBr addition to terminal alkynes 18 Scheme 21. Synthesis of 8 by bromination/dehydrobromination sequence...................... 19 Scheme 22. Preparation of tertiary α-bromoallylic alcohols via opening gem- dibromocyclopropanes .............................................................................................. 20 Scheme 23. Model reaction chosen for cryogenic reactor optimization........................... 23 Scheme 24. Synthesis of 1-bromo-1-lithioethene and trapping with acetone................... 29 Scheme 25. Material balance of 1-bromo-1-lithioethene (7) decomposition.................... 30 Scheme 26. Optimization of the deprotonation time for the synthesis of 7 ...................... 35 Scheme 27. Reactivity of bromoethene to n-BuLi versus t-BuLi..................................... 36 Scheme 28. Halogen-metal exchange versus deprotonation pathways for bromoethene . 37 Scheme 29. Calculated dimer/monomer equilibrium for 1-iodo-1-lithioethene............... 41 Scheme 30. Calculated dimer/monomer equilibrium for 7 solvated with THF................ 42 Scheme 31. Calculated energies of dissociation of solvated linear dimers of 7 ............... 43 Scheme 32. Intramolecular chelation of Li vs intermolecular chelation of Li in 7........... 45 Scheme 33. The synthesis of 7 in the presence of LiI....................................................... 46 Scheme 34. Calculated energetics for the formation of 18 ............................................... 47 Scheme 35. An initial attempt to trap 7 with a glucose-derived ketone............................ 51 Scheme 36. Preparation of ketone 38d.............................................................................. 56 vii Scheme 37. Potential usage of 7 in Physalin fragment synthesis.....................................
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