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Novel Methods for the Synthesis of Small Ring Systems Novel Methods for the Synthesis of Small Ring Systems David Stephen Pugh Thesis submitted in partial fulfilment of the requirements for the degree of Doctor of Philosophy University of York Department of Chemistry September 2011 Abstract Chapter 1 briefly reviews telescoped reactions, in particular tandem oxidation processes, detailing the background to the development of the methodology presented here, and sets out the aims for the Thesis. Chapter 2 reviews cyclopropanation methods and examines the preparation and use of triisopropylsulfoxonium tetrafluoroborate II for the preparation of gem- dimethylcyclopropanes for a range of α,β-unsaturated compounds including ketones, esters, amides, nitriles and nitro-compounds (Scheme I). Chapter 2 also examines potential applications for the methodology, outlining a route towards the synthesis of chrysanthemic acid as well as attempts towards rearrangement methodology. Scheme I: Chapter 3 demonstrates the preparation of 3-substituted oxindoles from substituted anilides in a copper-mediated cyclisation-decarboxylation sequence (Scheme II). Scheme II: This sequence is demonstrated for a range of alkyl, aryl and heteroaryl substituents in the 3-position, with methyl, benzyl and PMB protection on the nitrogen atom. Further development of the copper-cyclisation methodology leading to a catalytic system is presented, along with initial work towards a decarboxylative allylation of oxindoles. i Contents Abstract i Contents ii List of tables and figures v Acknowledgements vi Declaration vii Chapter 1: Telescoped reactions 1 1.1 Telescoped processes 1 1.1.1 Sequential and tandem reactions 1 1.2 Development of tandem oxidation processes 1 1.2.1 Tandem oxidation-Wittig processes 2 1.2.2 Tandem oxidation-alkyne formation 4 1.2.3 Telescoped oxidation-allylation processes 5 1.2.4 Tandem oxidation giving esters and amides 6 1.2.5 Tandem oxidation-imine formation 7 1.2.6 Tandem oxidation-nitrile formation 8 1.2.7 Formation of heterocycles 8 1.2.8 Tandem pyrazole formation-Suzuki coupling reactions 9 1.2.9 Tandem oxidation-cyclopropanation 10 1.3 Other telescoped processes 12 1.3.1 Telescoped approaches to oxindoles 12 1.4 Aims and objectives 13 Chapter 2: Preparation of gem-dimethylcyclopropanes 14 2.1 Cyclopropane functionality 14 2.1.1 Prevalence in nature 14 2.2 Synthesis of cyclopropanes 16 2.2.1 Wurtz type 16 2.2.2 Simmons-Smith type 16 2.2.3 From diazo compounds 17 2.2.4 From dichlorocarbenes 17 ii 2.2.5 Using ylides 18 2.2.6 Sulfur ylides 19 2.3 Synthesis of gem-dimethylcyclopropananes 22 2.3.1 Functional group conversion 22 2.3.2 Substrate approaches 22 2.3.3 Ylide approaches 23 2.3.4 Simmons-Smith approaches 24 2.3.5 Electrochemical approaches 25 2.3.6 Ring-contraction approaches 25 2.3.7 Intramolecular reactions 25 2.4 Ideas for a new reagent 26 2.4.1 Preparation of isopropyl sulfonium salts 27 2.4.2 Oxidation of sulfonium salts 29 2.4.3 Cyclopropanation of chalcone 61 31 2.5 Cyclopropanation with triisopropylsulfoxonium tetrafluoroborate 31 2.5.1 Initial synthesis of triisopropylsulfoxonium tetrafluoroborate 31 2.5.2 Reaction with chalcone 32 2.5.3 Preparation of chalcone analogues 34 2.5.4 Cyclopropanation of chalcone analogues 35 2.5.5 Cyclopropanation of esters and amides 38 2.5.6 Cyclopropanation of other substrates 40 2.5.7 Cyclopropanation of non-carbonyl Michael acceptors 42 2.5.8 Double cyclopropanations 43 2.5.9 Unsuccessful substrates 45 2.5.10 Development of the sulfoxonium salt synthesis 131 46 2.5.11 Attempts towards isopropyldiphenylsulfoxonium salts 131 50 2.5.12 Studies towards chrysanthemic acid 67 52 2.5.12.1 Chrysanthemic acid 67 53 2.5.12.2 Previous syntheses of chrysanthemic acid 67 54 2.5.12.3 Towards a new synthesis of chrysanthemic acid 67 56 2.6 Cyclopropane rearrangement 60 2.6.1 Previous approaches 60 2.6.2 Initial catalyst screening 61 2.6.3 Scope of rearrangement 66 iii 2.6.4 Rearrangement of methylene cyclopropanes 71 2.7 Future work 73 Chapter 3: Preparation of 3-alkyloxindoles 74 3.1 Oxindoles 74 3.1.1 Use as pharmaceuticals 75 3.2 Synthetic approaches 76 3.2.1 3-Substituted oxindoles 76 3.2.2 Isatin derived oxindoles 77 3.2.3 Reductive cyclisation 78 3.2.4 Alkylation of oxindole 79 3.2.5 Palladium coupling approaches 79 3.2.6 Friedel-Crafts approaches 82 3.2.7 Radical cyclisation 82 3.2.8 Oxidation of indoles 83 3.2.9 CH activation 84 3.3 Proposed methodology 86 3.3.1 Ethyl ester oxindoles 86 3.3.2 tert-Butyl ester oxindoles 88 3.3.3 Decarboxylation studies 90 3.3.4 Scope of methodology 92 3.3.5 Cleavable N-protecting groups 97 3.3.6 Methodology scale-up 99 3.3.7 Developments in the cyclisation 102 3.3.8 Preparation of 3-allyl-3-alkyl oxindoles 105 3.4 Summary and future work 108 Chapter 4: Experimental 110 4.1 General experimental 110 4.2 Preparation of gem-dimethylcyclopropanes 111 4.2.1 Preparation of sulfoxonium salts 111 4.2.2 Preparation of chalcones 118 4.2.3 Cyclopropanation of chalcones 128 4.2.4 Preparation of ester and amide substrates 138 iv 4.2.5 Cyclopropanation of esters and amides 140 4.2.6 Preparation of other substrates 144 4.2.7 Cyclopropanation of other substrates 150 4.2.8 Cyclopropanation of non-carbonyl Michael acceptors 151 4.2.9 Bis-cyclopropanation 153 4.2.10 Approaches towards chrysanthemic acid 67 157 4.3 Cyclopropane rearrangements 159 4.3.1 Rearrangement of gem-dimethylcyclopropanes 159 4.3.2 Preparation of methylene cyclopropanes 168 4.3.3 Rearrangement of methylene cyclopropanes 171 4.4 Preparation of oxindoles 174 4.4.1 Preparation of ethyl ester oxindoles 174 4.4.2 Preparation of tert-butyl ester oxindoles 178 4.4.3 Preparation of N-para-methoxybenzyl oxindoles 209 4.4.4 Preparation of N-benzyl oxindoles 215 4.4.5 Preparation of allyl ester oxindoles 219 Chapter 5: Publications 228 6.1 Chronological list of authored publications 228 6.2 Synlett 2008, 521-524. 230 6.3 Synthesis 2008, 3279-3288. 234 6.4 Acta Crystallogr. C, 2009, 65, o39-o41. 244 6.5 Synlett, 2010, 934-938. 247 6.6 Org. Lett., 2010, 12, 3446. 252 Appendix 1: X-ray crystal data for bis-cyclopropane 205 256 Abbreviations 277 References 282 v List of tables and figures Table 1: Preparation of chalcones 34 Table 2: Cyclopropanation of chalcones 36 Table 3: Cyclopropanation of esters 38 Table 4: Screening of oxidation conditions to give sulfoxonium salt 131 47 Table 5: Initial oxidation conditions 48 Table 6: Reduction of sulfonyl chloride 211 loadings 49 Table 7: Optimisation of the oxidation with barium hydroxide 50 Table 8: Catalyst screening for cyclopropane rearrangement 62 Table 9: Acid screening for the rearrangement of cyclopropane 62 65 Table 10: Rearrangement of chalcone-derived cyclopropanes 66 Table 11: Preparation of methylene cyclopropanes 71 Table 12: Rearrangement of methylene cyclopropanes 72 Table 13: Screening of dealkylation/decarboxylation conditions 90 Table 14: Alkylation of anilide 334 92 Table 15: Formation of tert-butyl oxindoles 94 Table 16: Dealkylation/decarboxylation of tert-butyl oxindoles 96 Figure 1: Structures of important compounds containing cyclopropanes 15 Figure 2: X-ray structure of cyclopropane 205 45 Figure 3: Unsuccessful cyclopropanation substrates 46 Figure 4: Chrysanthemic acid 67 53 Figure 5: Members of the pyrethroid family 53 Figure 6: Cyclopropanes for catalyst screening 61 Figure 7: Structure of an oxindole 74 Figure 8: Tryptophan 276 and auxins containing an indole core 74 Figure 9: Oxindole containing pharmaceuticals 75 vi Acknowledgements This thesis would not have been possible without the support of a great number of people. Firstly, to Professor Richard Taylor who gave me the opportunity to undertake a Ph.D, and provided much support and guidance through his supervision. To the many members of the Taylor group: Alan B, Alessia M, Alex C, Alexis P, Cat M, Dan H, Dave B, Graeme M, James C, James D, James R, Jan S, Jana L, Johannes K, Jon O, Katie G, Mark P, Melanie L, Mickael J, Mike E, Nicola C, Phil C, Pierre W, Reyhan B, Richard D, Richard P, Russ K, Sandra R, Stuart J, Subhrangsu R, Vilius F, Will B and Will U, who have all made working in the group an pleasure. In particular, I wish to thank Dr Mike Edwards for all his guidance, advice and proof reading the many drafts of this thesis, and to Graeme who looks after us all, maintaining every aspect of the labs. Thanks to all those contributing to technical services in the department: Steve, Mike, Derek and Val in stores; Trevor, Ben and Karl for mass spec; Adrian and Rob and the national crystallography service for X-ray; Phil and Graeme for microanalysis; and especially Heather and Amanda for the NMR service. Also thanks to the workshops (glass, electrical and mechanical) who put everything back together each time we break things and to the EPSRC and the University of York for funding. Thanks to all those who have contributed to providing distractions away from the lab, and particularly thanks to my family for their constant support and encouragement in everything I do. vii Declaration The research presented in this thesis was carried out at the University of York between October 2007 and September 2010. This work is, to the best of my knowledge, original, except where due reference has been made to other workers. David Stephen Pugh September 2011 viii Chapter 1 Chapter 1: Telescoped reactions 1.1 Telescoped processes A telescoped reaction involves multiple reaction steps occurring in one reaction vessel, with no intermediate work-up or purification, offering environmental advantages through reduced solvent usage and elimination of a workup/purification procedure.
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