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Conjugate Additions and Transposition of the Allylic Alcohols of Enol Ethers of 1, 2-Cyclohexanedione

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Conjugate Additions and Transposition of the Allylic Alcohols of Enol Ethers of 1, 2-Cyclohexanedione East Tennessee State University Digital Commons @ East Tennessee State University Electronic Theses and Dissertations Student Works 12-2010 Conjugate Additions and Transposition of the Allylic Alcohols of Enol Ethers of 1, 2-Cyclohexanedione. Barnabas Otoo East Tennessee State University Follow this and additional works at: https://dc.etsu.edu/etd Part of the Organic Chemistry Commons Recommended Citation Otoo, Barnabas, "Conjugate Additions and Transposition of the Allylic Alcohols of Enol Ethers of 1, 2-Cyclohexanedione." (2010). Electronic Theses and Dissertations. Paper 1748. https://dc.etsu.edu/etd/1748 This Thesis - Open Access is brought to you for free and open access by the Student Works at Digital Commons @ East Tennessee State University. It has been accepted for inclusion in Electronic Theses and Dissertations by an authorized administrator of Digital Commons @ East Tennessee State University. For more information, please contact [email protected]. Conjugate Additions and Transposition of the Allylic Alcohols of Enol Ethers of 1, 2- Cyclohexanedione ________________________________ A thesis presented to the faculty of the department of Chemistry East Tennessee State University In partial fulfillment of the requirements for the degree Master of Science in Chemistry _________________________________ by Barnabas Otoo December 2010 _________________________________ Dr. David Young, Ph.D, Chair Dr. Yu Lin Jiang, Ph.D Dr. Peng Sun, Ph.D Key words: α,β-unsaturated systems, enone, enolate, silane, transposition, nucleophile ABSTRACT Conjugate Additions and Transposition of the Allylic Alcohols of Enol Ethers of 1, 2- Cyclohexanedione by Barnabas Otoo A variety of protected enolic forms of 1, 2-cyclohexanedione was prepared as substrates for conjugate addition studies using organocopper reagents. The sequence involved the enol ether preparation via the enolate, alkylation with an organometalic reagent, and oxidative rearrangement with pyridinium chlorochromate followed by the conjugate addition reactions. Protection of 1, 2-cyclohexanedione was achieved by reacting with chloro tert-butyldimethyl silane and subjected to alkylation. Steric problems were encountered and so an alternative protective group the methoxymethyl acetal was prepared and studied. Alkylation of these derivatives was successful; however, the oxidation was problematic and although evidence for rearrangement was observed in one case, it did not provide the desired ketone. 2 DEDICATION I dedicate this research and thesis to the memory of my late father Rev. Clarence Asamatey Otoo. 3 ACKNOWLEDGEMENTS I am most grateful to the Almighty God through his son Jesus Christ for strength, grace, and love that has sustained me through my life and throughout the research period. I am also highly indebted to my research advisor Dr. David Young for allowing me to work in his lab and for constantly guiding and advising me throughout the period. A big and sincere thank you also goes to Dr. Waderska, Dr. Eagle, Dr. Ho, Dr. Jiang, Dr. Sun, Ms Susan Campbell, Mrs. Rasnick, Tom, and all faculty and staff of the chemistry department of ETSU for being there and guiding me when need arises. I am also very grateful to ETSU and the government and people of USA for affording me the opportunity to study at ETSU. I could not also have come this far without a supportive family. I acknowledge the commitment to my cause and constant prayers of my mum and siblings. God bless you. I also highly appreciate the prayers, support, and love given me by Dr. and Mrs. Nyarambi of the College of Education. Finally, I wish to recognize and appreciate the contributions and efforts of colleague graduate students, past and present, and the Ghanaian community in Johnson City towards my successful stay and study at ETSU. God bless you all. 4 CONTENTS Page ABSTRACT.....................................................................................................................................2 DEDICATION.................................................................................................................................3 ACKNOWLEDGEMENTS.............................................................................................................4 LIST OF SCHEMES.......................................................................................................................8 LIST OF ABBREVIATIONS..........................................................................................................9 CHAPTER 1. INTRODUCTION…………….…………...………….…...…………………………….10 α, β Unsaturated Systems …………………...………………...........................................10 Preparation of α, β Unsaturated Systems …………….………….………….…………...11 α, β-Unsaturated Systems Without Further Unsaturation.........................................12 By Oxidative Elimination of Hydrogen ...........................................................12 By Elimination of Halide from α-Halo Aldehydes ..........................................12 By Elimination of Halide from Alkoxy Enol Ethers and Thioenol Ethers ......12 By Elimination from β-Hydroxy and Alkoxy Aldehydes ................................12 Oxidation Of Alcohols And Their Equivalents ........................................................13 Aldol Condensations .................................................................................................13 Chemistry of α, β Unsaturated Systems.............................................................................13 1, 4 – Nucleophilic Additions............................................................................................14 Mechanism of Conjugate Addition…………………………………….……..........14 Examples of Conjugate Addition Reactions .............................................................14 1,2 – Nucleophilic Additions .............................................................................................15 Mechanism ................................................................................................................15 Examples……………………………………………………………………...........15 Rahut-Currier Reactions....................................................................................................16 Nazarov Cyclization Reaction...........................................................................................16 Examples...................................................................................................................16 PCC Mediated Rearrangement of Allylic Alcohols Generated From 1,2 –Nucleophilic Additions on α, β Unsaturated Systems.............................................................................17 Mechanism ................................................................................................................18 5 Examples……………………………………………………………………...........19 Protective Groups...........................................................................................................................19 Table of Examples of Hydroxyl Protective Groups…………………….........…….20 Objective Of Research...................................................................................................................21 Scheme of Work.......................................................................................................22 2. RESULTS AND DISCUSSION……………………………………………………………...23 The Silanes.........................................................................................................................23 Cuprate Methylation (1, 4 –Addition)......................................................................23 Methylation Followed by PCC Rearrangement Attempt..........................................23 Methoxy Methyl Protecting Group…………………………………………………...….24 Cuprate Addition ……………………………………………………………...…...25 Methylation Followed by PCC Rearrangement……………………...………….....25 Conclusion……………………………………………………………………………….28 3. EXPERIMENTAL…………………………………………………………………………….29 General Methods……………………………………………………………....................29 Synthesis of 1,2 – Cyclohexanedione………………………………………....................29 Synthesis of 2-[[(1,1-Dimethylethyl)dimethylsilyl]oxy]-2-cyclohexen-1-one ……...…..30 Synthesis of 2-[[(1,1-Dimethylethyl)dimethylsilyl]oxy]-1-methyl-2-cyclohexen-1-ol….30 Synthesis of 2-[[(1,1-Dimethylethyl)dimethylsilyloxy]-1-vinyl-2-cyclohexen-1-ol…….30 Synthesis of 2-(Methoxymethoxy)-2-cyclohexen-1-one………………….......................31 Synthesis of 2-(Methoxymethoxy)-1-methyl-2-cyclohexen-1-ol.....……….....................31 Synthesis of 2-(Methoxymethoxy)-1-vinyl-2-cyclohexen-1-ol…...………......................32 Synthesis of 2-Acetyloxy-1-methyl-2-cyclohexen-1-one..…………………....................32 REFERENCES ..............................................................................................................................34 APPENDICES ...............................................................................................................................38 1 Appendix A: HNMR of Compound IIIA in CDCl3 .........................................................38 13 Appendix B: C NMR of Compound IIIA inCDCl3 .........................................................39 1 Appendix C: HNMR of Compound VIA in CDCl3 .........................................................40 13 Appendix D: C NMR of Compound VIA inCDCl3……………………………………41 1 Appendix E: HNMR of Compound IIB in CDCl3………………………………………42 13 Appendix F: C NMR of Compound IIB in CDCl3 ............................................……….43 6 1 Appendix G: HNMR of Compound IIIB in CDCl3……………………………………..44
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