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A** 2' 0 11 Cnev\ CONJUGATE ADDITIONS AND REDUCTIVE TRANSFORMATIONS OF FULVENES AND 6-VINYLFULVENES A thesis submitted to the faculty of San Francisco State University A** In partial fulfillment of 3 (c the requirements for 2 ' 0 11 the Degree c n e v \ Master of Science In Chemistry: Organic Synthesis by Teresa de Jesus Ortega San Francisco, California August 2019 Copyright by Teresa de Jesus Ortega 2019 CERTIFICATION OF APPROVAL I certify that I have read Conjugate additions and reductive transformations of fulvenes and 6-vinylfulvenes by Teresa de Jesus Ortega, and that in my opinion this work meets the criteria for approving a thesis submitted in partial fulfillment of the requirement for the degree Master of Science in Chemistry: Organic synthesis at San Francisco State University. Ihsan Erden, Ph.D Professor in Chemistry Taro Amagata, Ph.D Professor in Chemistry Weiming Wu, Ph.D Professor in Chemistry CONJUGATE ADDITIONS AND REDUCTIVE TRANSFORMATIONS OF FULVENES AND 6-VINYLFULVENES Teresa de Jesus Ortega San Francisco, California 2019 Fulvenes are a group of cross-conjugated compounds that have been of interest due to their diverse chemical and physical properties. Since the discovery of fulvenes by Thiele in the 1900s, and improved synthetic methods, fulvene chemistry has been explored and applications in organometallic chemistry and natural product synthesis have been unveiled. Herein, we disclose our results on the reactions of fulvenes and 6-vinylfulvenes with carbon nucleophiles and reducing agents. For this study, the carbon nucleophiles selected includes the carbon acids nitromethane and ethyl nitroacetate, furthermore, the reducing agent consists of UAIH4. Moreover, selective diazene reduction of fulvenes has been explored in the hopes of gaining a convenient access to 1,2-dihydrofulvenes. Nitronate anion additions onto regular fulvenes proved to be highly dependent on the C6-substitution pattern of the fulvene: 6,6-disubstituted fulvenes gave spiro[2.4]hepta-4,6-dienes whereas with 6-monosubstituted fulvenes the cyclopropanation was not completed, giving rise to 1- and 2-substituted cyclopentadienes. Due to the improved preparative methods of 6- vinylfulvenes, their reactivity was examined with three nucleophiles because 6- vinylfulvenes have two electrophilic sites, at the C6 and C8 position. The nucleophilic additions onto 6-vinylfulvenes, for the most part, occurred by a 1,4-conjugate addition with the carbon nucleophiles and UAIH4, however, 1,2-additions were observed with a few 6- vinylfulvene derivatives. In addition, the vinyl cyclopentadiene isomers derived from 6- vinylfulvene with UAIH4 were employed towards the synthesis of 2-vinylsubstituted fulvenes and isolated in moderate to excellent yields. Moreover, fulvene diazene reduction occurred by a mono-selective endocyclic manner and 1,2-dihydrofulvenes were isolated in moderate to excellent yields. I certify that the abstract is a correct representation of the content of this thesis 'HntoM Q/tfaiA VfgfZQ V\ Chair, Thesis Committee Date ACKNOWLEDGEMENTS I would like to express my immense gratitude to my advisor Dr. Ihsan Erden for being an excellent mentor and for his pai ;nce, guidance, and encouragement. The many discussions we shared were insightful and filled with kind words of wisdom. I admire his enthusiasm for chemistry and I thank him for working with me to complete this manuscript. I would also like to thank the rest of my committee members; Dr. Taro Amagata and Dr. Weiming Wu for their support and genuine advice. In addition, I would like to thank Dr. Robert Yen, the director of the SFSU Mass Spectrometry Facility, for running all my samples. I would also like to express my gratitude to the exceptional SFSU chemistry department faculty form whom I have learned a great deal of my knowledge in chemistry. To my lab members, I had a pleasure working with everyone and I thank them for the constant support and encouragement. Last but not least, I am thankful for the unconditional support from my family and friends. v TABLE OF CONTENTS List of Table.................................................................................................................................vii List of Figures............................................................................................................................ viii List of Schemes.............................................................................................................................ix 1. Introduction................................................................................................... 1 1.1 Background..................................................................................................................1 1.2 General fulvene synthesis......................................................................... 8 1.3 6-Vinylfulvene synthesis.......................................................................................... 9 1.4 Proposed research projects..................................................................................... 11 2. Results and Discussion...........................................................................................................14 2.1 Nitronate anion additions onto 6-mono and 6,6-disubsituted fulvenes........... 14 2.2 Nucleophilic additions onto 6-vinylfulvenes....................................................... 20 2.2.1 6-Vinylfulvene reactions with carbon nucleophiles...........................21 2.2.2 LiAlH4 reduction of 6-vinylfulvenes....................................................27 2.2.3 Application of the vinyl cyclopentadiene isomers....................... 30 2.3 Diazene reduction of 6-mono and 6,6-disubstituted fulvenes........................... 34 3. Conclusion...............................................................................................................................37 4. Experimental Procedures....................................................................................................... 38 4.1 Nitronate anion reaction procedures with 6-mono and 6,6-disubsituted fulvenes .......................................................................................................................... 39 4.2 Nitronate anion and ethyl nitroacetate reaction procedures 6-vinylfulvenes 45 4.3 Procedures for LiAlH4 reduction of 6-vinylfulvenes.........................................49 4.4 Fulvene synthesis procedures with vinyl cyclopentadiene isomers..................53 4.5 Procedures for diazene reduction of 6-mono and 6,6-disubstituted fulvenes 55 Reference......................................................................................................................................57 LIST OF TABLES Table Page 1. Reaction of 6-mono and 6,6-disubstituted fulvenes with nitronate anions 15 2. Reaction of 6-vinylfulvenes with carbon acids ritromethane and ethyl nitoacetate................................................................................................................ 21 3. LiAlH4 reduction of 6-vinylfulvenes and one 6,6-disubstituted fulvenes.................................................................................................................... 28 4. Synthesis of 6,6-dimethyl-2-vinylsubsituted fulvene with vinyl cyclopentadiene isomers and acetone.................................................................. 31 5. 1,2-Dihydrofulvenes derived by diazene mono selective endocyclic reduction of fulvenes............................................................................................. 34 LIST OF FIGURES Figures Page 1. General fulvene structure along with the most stable resonance structure 1 2. The synthesis of the tricyclic compound 4 via intramolecular [4+2] cycloaddition under basic conditions.......................................................................3 3. The total synthesis of P-vetivone implementing a fulvene as the starting material..........................................................................................................................3 4. The formal total synthesis of loganin and sarracenin was achieved by an initial [2+2] ketene cycloaddition from 6-acetoxyfulvene................................... 4 5. Example of fulvenes as 1 gands and derivatives for cyclopentadinyl anion ligands found in organometallics chemistry.............................................................5 6. The three modes of reaction for 6-(chloromethyl)-6-methylfulvene..................6 7. The three condensation reactions methods available to prepare a variety of fulvenes with cyclopentadiene and ketones or aldehydes starting materials 8 8. A three-step method developed to prepare the parent 6-vinylfulvene and 6-methyl-6-vinylfulvene.................................................................................... 10 9. 6-Vinylfulvene labeled and displaying the potential 1,2- and 1,4-additions .... 13 10. The C6 and C8 carbon Py LUMO coefficients of four 6-vinylfulvenes........... 24 LIST OF SCHEMES Scheme Page 1. Resonance and generation of nitronate anion under basic conditions.............11 2. The Henry reaction and nitronate anion Michael addition reaction.................. 12 3. Nef reaction under strong acid conditions............................................................12 4. General chemical equation for the nitronate anion reaction with 6,6-disubstituted fulvenes......................................................................................... 14 5. Mechanism for 6-monosubstituted fulvenes with nitronate
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