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“Alkenyl Nonaflates from Carbonyl Compounds: New Synthesis, Elimination Reactions, and Systematic Study of Heck and Sonogashira Cross-Couplings”

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“Alkenyl Nonaflates from Carbonyl Compounds: New Synthesis, Elimination Reactions, and Systematic Study of Heck and Sonogashira Cross-Couplings” “Alkenyl nonaflates from carbonyl compounds: New synthesis, elimination reactions, and systematic study of Heck and Sonogashira cross-couplings” A thesis submitted to the Freie Universität Berlin for the degree of Dr. rer. nat. Faculty of Chemistry and Biochemistry 2009 Michael Alexander Kolja Vogel Department of Biology, Chemistry and Pharmacy FU Berlin 1. Gutachter: Prof. Dr. C. B. W. Stark 2. Gutachter: Prof. Dr. H.-U. Reißig Promotionsdatum: 19.06.2009 Contents Contents Contents 3 Abbreviations 7 Declaration and Copyright Statement 9 The Author 12 Acknowledgements 13 Abstract / Zusammenfassung 14 Introduction and Objective 16 Chapter 1 Alkenyl nonaflates from enolizable carbonyl precursors – 25 methodology, preparation, and elimination reactions 1.1. Purification of NfF and compatibility experiments with bases 26 1.2. Application of the internal quenching protocol for the 30 preparation of cyclic alkenyl nonaflates 1.3. Reactions of acyclic ketones with NfF and phosphazene bases 36 1.3.1 General remarks 36 1.3.2. Synthesis of alkynes: reactivity and selectivity 38 1.4. The formation of allenes 45 1.5. Conversion of aldehydes with NfF and phosphazene bases 50 1.5.1. Alkenyl nonaflate formation 50 1.5.2. Formation of terminal alkynes 52 1.6. Conclusions 54 Chapter 2 The alkenyl nonaflates in the Heck reaction – 56 methodology and reactivity 3 Contents 2.1. General remarks 57 2.2. Methodology and initial experiments 59 2.3. Systematic investigations 61 2.3.1. The solvent effect 61 2.3.2. The effect of different bases 65 2.3.3. The effect of additives 66 2.3.4. The effect of triphenylphosphine 71 2.3.5. Lower catalyst loading 73 2.3.6. A short discussion about the role of the solvent 74 2.4. A comparison of cyclopentenyl nonaflate, triflate and iodide 75 2.5. Conclusions 77 Chapter 3 The Heck coupling with alkenyl nonaflates: principles, 78 scope, and the proof of homogeneity 3.1. General remarks 79 3.2. The proof of homogeneity 80 3.3. The Heck reaction with alkenyl nonaflates 88 3.4. Difficulties and limitations 94 3.4.1. Reactions of 2-methyl propenyl nonaflate 42a with different olefins 94 3.4.2. The Heck reaction with aryl nonaflates 98 3.5. Conclusions 99 Chapter 4 One-pot cross-coupling reactions 101 4.1. General remarks 102 4.2. One-pot Heck reactions 103 4.3. One-pot Sonogashira reactions 110 4.4. Conclusions 115 4 Contents Chapter 5 Towards the total synthesis of Stenusin 117 5.1. Introduction 118 5.2. General reaction outline 121 5.3. Synthesis 122 5.3.1. Reductive alkylation 122 5.3.2. Oxidation 126 5.3.3. Synthesis of the alkenyl nonaflate 126 5.3.4. Heck cross-coupling methodology 126 5.3.5. Hydrogenation of the diene 131 5.4. Summary and outlook 132 Chapter 6 Key achievements and perspective 133 6.1. Key achievements 134 6.2. Perspective 137 Chapter 7 Experimental part 139 7.1. General 140 7.2. Procedures and analytical details 141 7.2.1. Reactions of Chapter 1 141 7.2.2. Reactions of Chapter 2 172 7.2.3. Reactions of Chapter 3 174 7.2.4. Reactions of Chapter 4 198 7.2.5. Reactions of Chapter 5 233 7.3. Optimization reactions for regioselective product formation 241 7.3.1. 1,1,2,2,3,3,4,4,4-Nonafluoro-butane-1-sulfonic acid 5-methyl- 242 cyclopent-1-enyl ester 28f 7.3.2. 1,1,2,2,3,3,4,4,4-Nonafluoro-butane-1-sulfonic acid 6-methyl- 243 5 Contents cyclohex-1-enyl ester 28g 7.3.3. Optimization reactions for the regioselective formation of the 245 terminal alkyne Tridec-1-yne 38a from Tridecan-2-one 37 7.4. Kinetic measurements 247 7.4.1. Variation of the catalyst loading 247 7.4.2. Poisoning experiments 248 7.4.3. Centrifugation 249 Chapter 8 References 251 6 Abbreviations Abbreviations Ac acetyl t-Bu tert-butyl BTEM Band-Target Entropy Minimization ca. circa cat. catalytic °C degrees Celsius cm-1 wavenumber DCE dichloroethane DCM dichloromethane DMF dimethylformamide DMSO dimethylsulfoxide EI electron ionisation ESI electrospray ionisation Et ethyl et al. et alia eq. or equiv. equivalent GC gas chromatography GC-MS gas chromatography–mass spectrometry GP general procedure h hour HPLC high performance liquid chromatography HR high resolution ICES Institute of Chemical and Engineering Sciences IR infrared J NMR coupling constant lit. literature M molar MCPBA meta-chloroperbenzoic acid MeCN acetonitrile MHz megahertz min. minute ml millilitre(s) mmol millimole(s) 7 Abbreviations m.p. melting point MS mass spectroscopy N normal NMR nuclear magnetic resonance NMR data: s singlet d doublet dd double doublet ddd double double doublet t triplet dt double triplet quart. quartet quint. quintet m multiplett Ph phenyl ppm parts per million Pr propyl quant. quantitative R unspecified group RAMP (R)-1-amino-2-methoxymethylpyrrolidine rpm revolutions per minute r.t. room temperature SAMP (S)-1-amino-2-methoxymethylpyrrolidine STAB-H sodium triacetoxy borohydride TEMPO 2,2,6,6-tetramethylpiperidine-1-oxyl tert tertiary TBAF tetra n-butylammonium fluoride TBDMS tert-butyldimethylsilyl TFA trifluoroacetic acid THF tetrahydrofurane TLC thin layer chromatography TMS trimethylsilyl 8 Declaration and Copyright Statement Declaration and Copyright Statement The laboratory work for this thesis was carried out between August, 2004 and August, 2007 at ICES Ptd Ltd Singapore. The thesis was written within the period of October, 2007 to April, 2009. The thesis was composed unassisted. No portion of the referred to in this thesis has been submitted in support of an application for another degree or qualification of this or any other university or institute of learning. Copyright in text of this thesis rests with the Author. Copies (by any process) either in full, or of extracts, may be made only in accordance with instructions given by the Author and lodged in the library of Freie Universität Berlin. Details may be obtained from the Librarian. This page must form part of any such copies made. Further copies (by any process) of copies made in accordance with such instructions may not be made without the permission (in writing) of the author. The ownership of any intellectual property rights which may be described in this thesis is vested in ICES Ptd Ltd, Singapore, subject to any prior agreement to the contrary, and may not be made available for use by third parties without the written permission of the Institute, which will prescribe the terms and conditions of any such agreement. Further information on the conditions under which disclosures and exploitation may take place is available from the head of ICES Ptd Ltd. 9 Declaration and Copyright Statement In parts results described within this thesis have been published so far in peer reviewed journals or were presented on conferences as posters or oral presentations. Publications in peer reviewed journals: 4.) Thieme Chemistry Journal Awardees – Where are they now? “A General One-Step Synthesis of Alkynes from Enolisable Carbonyl Compounds”; Ilya M. Lyapkalo, Michael A. K. Vogel, Ekaterina V. Boltukhina, Jiri Vavrik, Synlett, 2009, 4, 558-561. 3.) “A Straightforward Synthesis of Alkenyl Nonaflates from Carbonyl Compounds Using Nonafluorobutane-1-sulfonyl Fluoride in Combination with Phosphazene Bases”; Michael A. K. Vogel, Christian B. W. Stark and Ilya M. Lyapkalo, Synlett, 2007, 18, 2907-2911. 2.) “An Expedient Variant of Heck Reaction of Alkenyl Nonaflates: Homogeneous Ligand-Free Palladium Catalysis at Room Temperature”; Michael A. K. Vogel, Christian B. W. Stark and Ilya M. Lyapkalo, Adv. Synth. & Catal., 2007, 349, 7, 1019-1024. 1.) “A General and Versatile Method for C-C Cross-Coupling Synthesis of Conjugated Enynes: One-Pot Sequence Starting from Carbonyl Compounds”; Ilya M. Lyapkalo and Michael A. K. Vogel, Angew. Chem., 2006, 118, 4124–4127; Angew. Chem. Int. Ed. 2006, 45, 4019–4023. Oral or poster presentations: 9.) Michael A. K. Vogel, Christian B. W. Stark, Ilya M. Lyapkalo; “A New General One- step Methodology for the Synthesis of Alkynes from Enolizable Carbonyl Compounds”; 8th Tetrahedron Symposium; Berlin, 2007, Poster presentation. 8.) Michael A. K. Vogel, Ilya M. Lyapkalo; “A New Expedient Variant of Heck Reaction of Alkenyl Nonaflates: Homogeneous Ligand- and Additive-free Pd-catalysis at Room Temperature”; German-Singapore Symposium; Singapore, 2007, Oral presentation. 7.) Michael A. K. Vogel, Ilya M. Lyapkalo; “A New Expedient Variant of Heck Reaction of Alkenyl Nonaflates: Homogeneous Ligand- and Additive-free Pd-catalysis at Room 10 Declaration and Copyright Statement Temperature”; Asia Pacific Congress on Catalysis (APCAT-4); Singapore, 2006, Oral presentation. 6.) Michael A. K. Vogel, Ilya M. Lyapkalo; “A Straightforward Synthesis of Alkenyl Nonaflates from Carbonyl Compounds using Nonafluorobutane-1-sulfonylfluoride in Combination with Phosphazene Bases.”; International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC – 10); Kyoto, 2006, Poster presentation. 5.) Michael A. K. Vogel, Ilya M. Lyapkalo; “A New Expedient Variant of Heck Reaction of Alkenyl Nonaflates: Homogeneous Ligand- and Additive-free Pd-catalysis at Room Temperature”; International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC – 10); Kyoto, 2006, Oral presentation. 4.) Michael A. K. Vogel, Ilya M. Lyapkalo; “Alkenyl Nonaflates as a new entry in Transition Metal Catalysis - Highly robust and efficient ligand-free Heck Coupling Protocol starting from Carbonyl Precursors”; 231st ACS National Meeting, Atlanta, 2006, Oral Presentation. 3.) Michael A. K. Vogel, Ilya M. Lyapkalo; “Alkenyl Nonaflates as a new entry in Transition Metal Catalysis - Highly robust and efficient ligand-free Heck Coupling Protocol starting from Carbonyl Precursors”; SICC-4 (Singapore International Chemical Conference – 4), Singapore, 2005, Oral Presentation. 2.) Michael A. K. Vogel, Ilya M. Lyapkalo; “Alkenyl Nonaflates as a New Entry in Transition Metal Catalysis: Highly Robust, Fast and Efficient Ligand-free Heck Coupling Protocol at Ambient Temperature.”; C&FC 2004 (International Symposium on Catalysis and Fine Chemicals 2004), HongKong, Poster Presentation.
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