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Corrole Synthesis and Catalytic Applications Toward Cobalt(III)- Catalyzed Epoxidation, N-H Insertion, and Cyclopropanation

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Corrole Synthesis and Catalytic Applications Toward Cobalt(III)- Catalyzed Epoxidation, N-H Insertion, and Cyclopropanation University of South Florida Scholar Commons Graduate Theses and Dissertations Graduate School 12-31-2010 Corrole Synthesis and Catalytic Applications Toward Cobalt(III)- Catalyzed Epoxidation, N-H Insertion, and Cyclopropanation Chung Sik Kim University of South Florida Follow this and additional works at: https://scholarcommons.usf.edu/etd Part of the American Studies Commons, and the Chemistry Commons Scholar Commons Citation Kim, Chung Sik, "Corrole Synthesis and Catalytic Applications Toward Cobalt(III)-Catalyzed Epoxidation, N- H Insertion, and Cyclopropanation" (2010). Graduate Theses and Dissertations. https://scholarcommons.usf.edu/etd/3459 This Dissertation is brought to you for free and open access by the Graduate School at Scholar Commons. It has been accepted for inclusion in Graduate Theses and Dissertations by an authorized administrator of Scholar Commons. For more information, please contact [email protected]. Corrole Synthesis and Catalytic Applications Toward Cobalt (III)-Catalyzed Epoxidation, N-H Insertion, and Cyclopropanation by Chung Sik Kim A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy Department of Chemistry College of Arts and Sciences University of South Florida Major Professor: X. Peter Zhang, Ph.D. Jon Antilla, Ph.D. Roman Manetsch, Ph.D. Mark McLaughlin, Ph.D. Date of Approval: Oct 20, 2010 Keywords: Corroles, Cobalt(III) Complex, Epoxidation, N-H Insertion, and Cyclopropanation Copyright © 2010, Chung Sik Kim Special Thanks To my God To my lovely wife To my endless supporter, Mom To my late father TABLE OF CONTENTS LIST OF TABLES iii LIST OF FIGURES iv LIST OF SCHEMES v LIST OF ABBREVIATIONS vi ABSTRACT viii CHAPTER I: INTRODUCTION .........................................................................................1 CHAPTER II: SYNTHESES OF CORROLES ...................................................................8 General introduction ..........................................................................................8 Corrole synthesis ................................................................................................9 Chiral corrole synthesis....................................................................................14 Cobalt(III) corrole synthesis ............................................................................15 Conclusions ......................................................................................................16 General procedure for synthesis of brominated corroles .................................17 References ........................................................................................................30 CHAPTER III: COBALT CORROLE CATALYZED EPOXIDATION REACTIONS OF ALDEHYDES WITH ETHYL PHENYLDIAZOACETATE .............31 General introduction ........................................................................................31 Epoxidation reaction using cobalt(III) corrole as a catalyst ............................34 Conclusions ......................................................................................................43 Experimental data for epoxidation reactions ..................................................47 i References ........................................................................................................55 CHAPTER IV: COBALT CORROLE CATALYZED N-H INSERTION REACTIONS WITH DIVERSE DIAZO REAGENTS ....................................................57 General Introduction ........................................................................................57 N-H insertion reactions using cobalt(III) corroles ...........................................59 Conclusions ......................................................................................................65 Experimental data for N-H insertion reactions ................................................69 References ........................................................................................................78 CHAPTER V: COBALT CORROLE CATALYZED CYCLOPROPANATION REACTIONS OF VINYL ETHERS WITH α- NITRODIAZOACETATE ...................................................................80 General introduction ........................................................................................80 Cyclopropanation reactions using cobalt(III) corroles ....................................81 Asymmetric cyclopropanation reaction using chiral cobalt(III) corroles ........86 Conclusions ......................................................................................................88 Experimental data for cyclopropanation reactions ..........................................92 References ........................................................................................................97 APPENDIX A: 1H AND 13C NMR SPECTRA OF SELECTED COMPOUNDS ..........100 APPENDIX B X-RAY CRYSTALLOGRAPHIC DATA FOR COMPOUND 37 ........162 ii LIST OF TABLES Table 3.1 Reaction of phenyl diazoacetate with aldehydes 32 Table 3.2 Co(III) corrole-catalyzed epoxidation reactions 38 Table 3.3 Axial ligand effects on epoxidation reactions 42 Table 4.1 [RuCl2(p-cymene)]2-catalyzed intermolecular carbenoid N-H insertion reactions with amines and amides 58 Table 4.2 Intermolecular N-H insertion of aniline with ethyl phenyldiazoacetate by Co(III) corroles 61 Table 4.3 [Co(C1)CNtBu]-Catalyzed N-H insertion reaction of aniline with diverse Diazo reagents 62 Table 4.4 [Co(C1)CNtBu]-catalyzed N-H insertion reactions using amines and amides 63 Table 5.1 [Co(C1)PPh3]-catalyzed cyclopropanation of different vinyl ethers with α- nitrodiazoacetatee 83 iii LIST OF FIGURES Figure 1.1 Structure of a) porphyrin, b) corrole, and c) corrin 1 Figure 1.2 Number of corrole-related publications from 1955 to 2010 2 Figure 2.1 Structure of dipyrromethane 3, N-confused dipyrromethane 4, tripyrrane 5 11 Figure 3.1 Structures of metalloporphyrin and corrole catalysts 35 Figure 3.2 Crystal structures of ethyl 2(4-bromophenyl)-3-phenyloxirane-2-carboxylate 37 41 Figure 4.1 Structures of metalloporphyrin and corrole catalysts 60 Figure 5.1 Structures of metalloporphyrins and corrole catalysts 82 iv LIST OF SCHEMES Scheme 2.1 Preparation of 2,6-dibrombenzaldehyde 1 via metalation of 1,3- Dibromobenzene 10 Scheme 2.2 Synthesis of dipyrromethane 2 10 Scheme 2.3 Brominated corrole synthesis with dipyrromethane 2 and diverse aldehydes 12 Scheme 2.4 Synthesis of various brominated corroles 13 Scheme 2.5 Synthesis of chiral corroles 14 Scheme 2.6 Synthesis of Co(III) corrole complexes 15 Scheme 3.1 General mechanism of epoxidation using Rh(OAc)2 32 Scheme 3.2 Epoxidation reactions of aldehydes with diazo reagents 34 Scheme 3.3 Epoxidation of aldehydes with ethyl phenyldiazoacetate by metallocorroles 36 Scheme 3.4 Proposed mechanism of epoxidation reaction using Co(III) corrole 43 Scheme 4.1 Intermolecular N-H insertion via a metal-catalyzed decomposition of diazoacetate 57 Scheme 4.2 One pot two reactions using α-aldehyde diazoacetate with anilins using [Co(C1)CNtBu] 65 Scheme 5.1 Cyclopropanation of vinyl ether with α- nitrodiazoacetate catalyzed by Co(III) corrole 82 Scheme 5.2 Proposed mechanism of cyclopropanation of vinyl ethers with α- nitrodiazoacetate using Co(III) corrole 86 Scheme 5.3 Comparative reaction screening using chiral Co(III) corroles 87 Scheme 5.4 Asymmetric cyclopropanation reactions using chiral Co(III) corroles 88 v LIST OF ABBREVIATIONS Boc = tert-butoxycarbonyl [Co(P1)] = Cobalt(II) tetraphenyl porphyrin [Co(P2)] = Cobalt(II) 10, 20-(3,5-ditertbutylphenyl)-5,15-(2,6-dibromophenyl)porphyrin. [Co(C1)PPh3] = [Cobalt(III)(10-(3,5-di-tert-butylphenyl)-5,15-(2,6- dibromophenyl))corrole(PPh3)] [Co(C1)tBuNC] = [Cobalt(III)(10-(3,5-ditertbutylphenyl)-5,15-(2,6- dibromophenyl))corrole(tBuNC)] DCC = N’,N'-dicyclohexylcarbodiimide DCM = Dichloromethane DMF = N’,N’-Dimethyl formamide DMSO = Dimethylsulfoxide DSSCs = Dye-sentitized solar cells EDA = Ethyl diazoacetate ESI = Electrospray ioninzation FTIR = Fourier transform infrared EtOAc = Ethyl acetate HCl = Hydrochloric acid LDA = Lithium diisopropylamide MDA = α-methyl diazoacetate vi NDA = α-nitro diazoacetate p-CHLORANIL = 2,3,5,6-tetrachlorocyclohexa-2,5-diene-1,4-dione PDA = Ethyl phenyldiazoacetate PPh3 = Triphenylphosphine TEA = Triethylamine TFA = Trifluoroacetic acid THF = Tetrahydrofuran TLC = Thin layer chromatography TMS = Tetramethylsilane TOF = Time-of-flight vii ABSTRACT A variety of bromocorroles, useful precusors for Pd-based cross coupling, were sucessfully synthesized in moderate to good yields. Chiral corroles were also synthesized through use of chiral amides in the aforementioned cross coupling reactions. Cobalt complexes bearing π- t acceptor (CN Bu) and σ-donor (PPh3) ligands were also prepared in excellent yields. In this dissertation, cobalt (III) corrole complexes were applied to three different reaction areas: epoxidation, N-H insertion, and cyclopropanation. Cobalt(III) corroles were found to be efficient catalysts for epoxidation reactions. The epoxidation reactions can be carried out using ethyl phenyldiazoacetate, an acceptor/donor diazo compound, as a carbenoid precusor. The reaction provided highly diastereoselective epoxides. In addition to epoxidation, N-H insertion reactions using cobalt(III) corroles as catalysts smoothly produced the desired products with diverse diazo reagents. The reactions were screened using ethyl phenyldiazoacetate with a selection of anilines and amides. In order to investigate
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