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(Metal = Iridium(Iii) and Gold(Iii)) Bond METAL–CARBON (METAL = IRIDIUM(III) AND GOLD(III)) BOND FORMATION UNDER TRANSMETALATION AND CATALYTIC CONDITIONS; METALLONUCLEOSIDES AS ANTICANCER DRUGS AND BIO-PHOTONIC PROBES; AND SYNTHESIS OF IRIDIUM FLUORIDE COMPLEXES By AYAN MAITY Submitted in partial fulfillment of the requirements for the Degree of Doctor of Philosophy Thesis Advisor: Thomas G. Gray, Ph.D. Department of Chemistry CASE WESTERN RESERVE UNIVERSITY January 2015 CASE WESTERN RESERVE UNIVERSITY SCHOOL OF GRADUATE STUDIES We hereby approve the thesis/dissertation of Ayan Maity candidate for the Doctor of Philosophy degree*. (signed) Irene Lee, Ph.D. (Chair of the committee) Thomas G. Gray, Ph. D. Malcolm E. Kenney, Ph.D. James D. Burgess, Ph.D. Horst von Recum, Ph.D. (date) 6th August, 2014 * We also certify that written approval has been obtained for any proprietary material contained therein. ii Dedicated to all my teachers who taught me to love the subject and inspired me to decipher the mysteries of chemistry, specially Prof. Prasanta Ghosh and Prof. Ashish Kumar Nag; and to my loving uncle ‘Chotomama’ iii TABLE OF CONTENTS TABLE OF CONTENTS iv LIST OF FIGURES ix LIST OF SCHEMES xiv LIST OF TABLES xv LIST OF CHARTS xviii ACKNOWLEDGEMENT xix LIST OF ABBREVIATIONS xxi ABSTRACT xxvi Chapter 1. General Introduction 1 1.1. The Chemistry of Iridium 2 1.2. The Chemistry of Gold 7 1.3. Transmetalation Synthesis of Cyclometalated Iridium(III) Complexes 12 1.4. 2-Deoxy-Ribose Sugar Complex of Cyclometalated Iridium(III): Probe for Nucleosides Transporter 15 1.5. Transition Metal Fluorine Chemistry 18 1.6. Gold(I) Based Anticancer Drugs 20 1.7. Proposed Research 25 A. Application of Transmetalation Strategy to Synthesize Cyclometalated Iridium(III) Complexes 25 B. Suzuki–Miyaura Coupling of Arylboronic Acids to Gold(III) 26 iv C. Cyclometalated Iridium(III) Complexes with Deoxyribose Substituents 27 D. Synthesis of Bridging and Terminal Cyclometalated Complexes of Iridium(III) 28 E. A Gold(I) Metallonuceloside as Anticancer Drug 30 1.8. References 31 Chapter 2. Application of Transmetalation Strategy to Synthesize Cyclometalated Iridium(III) Complexes 42 2.1. Introduction 43 2.2. Results and Discussion 48 2.3. Conclusion 57 2.4. Experimental Section 57 2.4.1. Materials and Methods 57 + 2.4.2. Synthesis of Bis-aquo Complexes [L2Ir(H2O)2] (a-e) 58 2.4.3. Synthesis of C^N Chelating Borylated Ligands 60 2.4.4. Base Promoted Transmetalation Reactions 62 2.4.4.1. Synthesis of Iridium Complexes With C^N Chelating Ligands 62 2.4.4.2. Synthesis of Iridium Complexes with C^O Chelating Ligands 71 2.4.5. Luminescence Measurements 82 2.5. References 82 Chapter 3. Suzuki–Miyaura Coupling of Arylboronic Acids to Gold(III) 87 v 3.1. Introduction 88 3.2. Results and Discussion 89 3.3. Conclusion 100 3.4. Experimental Section 102 3.4.1. Materials and Methods 102 3.4.2. Synthesis of [(C^N)AuCl2] 103 3.4.3. Synthesis of [(tpy)Au(aryl)2] 105 3.4.4. Synthesis of monoarylated products 119 3.5. References 122 Chapter 4. Cyclometalated Iridium(III) Complexes with Deoxyribose Substituents 127 4.1. Introduction 128 4.2. Results and Discussion 131 4.3. Conclusion 136 4.4. Experimental Section 137 4.4.1. Materials and Methods 137 4.4.2. Synthesis of ligandoside 138 4.4.3. Synthesis of metallonucleosides 141 4.4.4. Luminescence Measurements 145 4.5. References 146 Chapter 5. Synthesis and Reactivity of Bridging and Terminal Fluoride Complexes of Bis(cyclometalated) Iridium(III) 153 5.1. Introduction 154 vi 5.2. Results and Discussion 156 5.3. Conclusion 164 5.4. Experimental Section 164 5.4.1. Materials and Methods 164 5.4.2. Synthesis of Fluoride Bridged Ir(III) Cyclometalates 166 5.4.3. Synthesis of Terminal Fluoride Complexes of Ir(III) Cyclometalates 167 5.4.4. Reactivity of [Ir(bt)2(F)(3,5-dimethylpyrazole)] (2a) with Silylated Reagents 169 5.4.5. Fluorine Transfer Reaction with Carbon and Sulfur Based Electrophile 173 5.4.6. X-ray Crystallography 174 5.4.7. Luminescence Measurements 174 5.5. References 175 Chapter 6. Synthesis and Cytotoxicity Studies of a Non-natural Nucleoside Bearing (triphenylphosphine)gold(I) 179 6.1. Introduction 180 6.2. Results and Discussion 182 6.2.1. Synthesis 182 6.2.2. Cytotoxicity Studies 185 6.2.3. Flow-cytometric Analysis 189 6.2.4. Apoptosis Measurement 191 6.2.5. Mitochondrial Permeability Transition 192 vii 6.2.6. Inhibition of Thioredoxin Reductase (TrxR) 193 6.3. Conclusion 195 6.4. Experimental Section 195 6.4.1. Materials and Methods 195 6.4.2. Synthesis of gold(I) nucleosides 196 6.4.3. General Cell Culture Procedures 201 6.4.4. Cell Proliferation Assays 201 6.4.5. Measurements of Apoptosis 202 6.4.6. Cell Cycle Analyses 202 6.4.7. Assessment of the Mitochondrial Membrane Potential 203 6.4.8. Thioredoxin Reductase Inhibition 204 6.5. References 204 Chapter 7. Conclusion And Future Direction 207 Appendix 211 Bibliography 324 viii LIST OF FIGURES Figure 1.1.1. Energy transfer mechanisms in the sensitized system. 5 Figure 1.1.2. Structure of facial-tris(2-phenylpyridinato,N,C2′)iridium(III), fac-Ir(ppy)3. 6 Figure 1.2.1. Position of gold in periodic table of elements. 7 Figure 1.2.2. Aurophilic interaction in dithiocarbamate complexes of gold(I). 11 Figure 1.4.1. Nucleoside transport processes in mammalian cells. 17 Figure 1.5.1. Electronic properties of halide ligands. 19 Figure 1.6.1. Structure of rheumatoid arthritis drug auranofin and proposed radiosensitizer. 22 Figure 1.6.3. Organophosphines and their cone 23 Figure 1.6.2. Models for the cytotoxic effects of gold-containing nucleosides. 24 Figure 2.1.1. Energy diagram for the working principle of OLEDs. 45 Figure 2.1.2. Crystal structure of the aldehyde complex [(F2ppy)2Ir(FoTol)] showing ellipsoids at the 50% probability level. 54 Figure 2.1.3. Crystal structure of the alcohol complex [(F2ppy)2Ir(TolMeOH)] showing 50% probability ellipsoids. 55 Figure 2.1.4. UV-vis absorption and emission spectra of [(F2ppy)2Ir(FoTol)] in deaerated acetonitrile. 56 Figure 3.2.1. a) Crystal structure of [(tpy)Au(p-C6H5F)2], b) Crystal structure of [(tpy)Au(4-(trifluoromethyl)phenyl)2], c) Crystal structure of [(tpy)Au(3- nitrophenyl)2]. 95 Figure 3.2.2. a) Crystal structure of disordered [(tpy)Au(benzo[b]thien-2- 96 ix yl)2], b) Crystal structure of [(tpy)Au(o-tolyl)2]. Figure 3.2.3. a) Crystal structure of [(tpy)Au(4-isopropoxyphenyl)2], b) Crystal structure of [(tpy)Au(Cl)( 4-fluorophenyl)], c) Crystal structure of [(tpy)Au(Cl)(1-naphthyl)]. 97 Figure 3.2.4. Crystal structure of dichloro(2-(4- fluorophenyl)pyridine)gold(III) 98 Figure 3.2.5. Crystal structure of [(tpy)Au(2-acetylphenylato)]. 99 Figure 4.2.1. Thermal ellipsoid representation (50% probability) of the cation of [Ir(ppy)2(7)](PF6). 133 Figure 4.2.1. (a) Absorption spectra of metallonucleosides collected in acetonitrile solvent at 298K; (b) Normalized emission spectra (298 K) of new complexes in 2-methyltetrahydrofuran. 134 Figure 4.2.3. Normalized emission spectra (77 K) of new complexes in 2- methyltetrahydrofuran glass. 135 Figure 5.2.1. Crystal structure of the iridium(III) dimer [(bt)2Ir(µ-F)]2 (50%). 157 Figure 5.2.2. Crystal structure of [Ir(bt)2(F)(3,5-dimethylpyrazole)] (50% probability). 158 Figure 5.2.3. a) Crystal structure of [Ir(bt)2(Cl)(3,5-dimethylpyrazole)] (50% probability). b) Crystal structure of [Ir(bt)2(SPh)(3,5-dimethylpyrazole)] (50% probability). c) Crystal structure of [Ir(bt)2(N3)(3,5-dimethylpyrazole)] (50% probability). 160 Figure 5.2.4. Normalized, room-temperature emission spectra of [(bt)2Ir(µ- F)]2 (solid) and [Ir(bt)2(F)(3,5-dimethylpyrazole)] (dashed) in 2- 163 x methyltetrahydrofuran. Figure 6.1.1. Clinically established gold(I) anti-arthritic drugs. 181 Figure 6.1.2. Designing of gold(I) containing nucleoside. 182 Figure 6.2.1. Synthesized gold(I) containing nucleosides. 184 Figure 6.2.2. Crystal structure of the complex (9-(2-deoxy-β-D-erythro- pentofuranosyl)purine-6-thio)(tricyclohexylphosphine) -gold- (I), 8b showing ellipsoids at the 50% probability level. 185 Figure 6.2.3. CCRF CEM-7 cell proliferation after different concentration of drug treatment over 48 h. Compound 7 is represented as dR-MP and compound (9-(2-deoxy-β-D-erythro-pentofuranosyl)purine-6- thio)(triphenylphosphine)gold- (I) (8a) as dR-MP-AuPPh3. 186 Figure 6.2.4. Drug sensitivity profile of CCRF CEM-7 cells treated with 7 and 8a for 48 h. Compound 7 is represented as dR-MP and compound 8a as dR-MP-AuPPh3. 186 Figure 6.2.5. Cytotoxicity of 8a on Molt 4 cells after 48 h. Compound 8a as dr-MP-AuPPh3. 187 Figure 6.2.6. Induction of cell cycle arrest in the Molt 4 cancer cells after treatment with compound 7 and compound (9-(2-deoxy-β-D-erythro- pentofuranosyl)purine-6-thio)(triphenylphosphine)gold- (I), 8a. 190 Figure 6.2.7. Annexin-PI staining of Molt 4 cells treated with compound 8a for 48 hr. 191 Figure 6.2.8. Mitochondrial permeability transition assay performed with HeLa cells. 192 xi Figure 6.2.9. The time course vs absorbance plot for thioredoxin reductase inhibition assay when treated with two different concentratopn of compound 8a along with positive (marked as DTNB+TrXR in the graph) and negative control (marked as DTNB control). 194 Figure 7.1. Various cyclometalating ligand that are available.
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