Bioorganometallic Chemistry (Topics in Organometallic Chemistry, 17)

Bioorganometallic Chemistry has become a mature area of science and is comprehensively covered by leading experts in this book. Naturally occuring bioorganometallic complexes, such as vitamin B 12 and recently discovered iron and nickel hydrogenases, including a possible role of the latter in the geochemical theory of the origin of life, are considered. The possible formation of carbene complexes of cytochrome P450 enzymes in various metabolisms of xenobiotics is also discussed. The bioorganometallic chemistry is considered to provide not only organometallic receptors such as polynuclear organometallic macrocycles for biologically interesting molecules but also ferrocene-peptide bioconjugates giving a peptidomimetic basis for protein folding. The medicinal properties of organometallic compounds are reviewed, with notable applications in the treatment and diagnosis of cancer and in the treatment of viral, fungal, bacterial and parasitic infections. Therefore the reader will get a balanced view of this rapidly developing and promising area. Cover Page 1 Topics in Organometallic Chemistry 3 Title Page - Bioorganometallic Chemistry 4 ISBN 354033047X 5 Volume Editor 6 Editorial Board 6 Topics in Organometallic Chemistry Also Available Electronically 7 Preface 8 Contents (with page links) 10 Biological Organometallic Chemistry of B12 12 1 Introduction 13 2 B12: Structure and Reactivity 15 2.1 Crystallographic Structural Studies 15 2.2 Structural Studies of B12-Derivatives by Nuclear Magnetic Resonance Spectroscopy 22 3 B12-Electrochemistry 24 3.1 Thermodynamic Redox Properties of Cobamides 25 3.2 Kinetic Redox Properties of Cobamides 28 3.3 Organometallic Electrochemical Synthesis 30 4 Reactivity of B12-Derivatives in Organometallic Reactions 31 5 Occurrence and Structure of Natural Corrinoids 37 6 B12-Dependent Methyl Transferases 38 6.1 Methionine Synthase 40 6.2 B12-Cofactors in Enzymatic Methyl-Group Transfer 41 7 Coenzyme B12-Dependent Enzymes 42 7.1 Carbon Skeleton Mutases 45 7.1.1 Methylmalonyl-CoA Mutase 45 7.1.2 Glutamate Mutase 47 7.1.3 Other B12-Dependent Carbon Skeleton Mutases 49 7.2 Diol Dehydratases and Ethanolamine Ammonia Lyase 50 7.3 B12-Dependent Amino Mutases 52 7.4 B12-Dependent Ribonucleotide Reductase 52 7.5 B12-Coenzymes in Enzymatic Radical Reactions 53 8 B12-Dependent Reductive Dehalogenases 54 9 B12 in Toxicology and Medicine 55 9.1 Toxicology 55 9.2 Medical Aspects 57 References 58 Catalytic Nickel–Iron–Sulfur Clusters: From Minerals to Enzymes 68 1 Introduction 68 2 Mineral FeS and NiFeS Clusters 70 3 NiFeS Clusters in Enzymes 73 3.1 [NiFe] Hydrogenases 74 3.2 Nickel-Containing Carbon Monoxide Dehydrogenases 77 3.3 Acetyl Coenzyme A Synthases 79 4 Catalytic Mechanisms 82 5 Conclusions 89 References 89 Carbene Complexes of Heme Proteins and Iron Porphyrin Models 94 1 Introduction 95 2 Overview: Carbenes as Ligands to Heme Proteins 96 2.1 Cytochrome P450 96 2.2 Myoglobin and Hemoglobin 102 3 Carbenes as Ligands to Iron Porphyrins 103 3.1 General 103 3.2 Syntheses 105 3.3 X-ray Structures and Spectroscopic Characterizations 110 3.4 Reactivity 112 4 Carbenes as Ligands to Ruthenium and Osmium Porphyrins 114 4.1 Ruthenium 114 4.2 Osmium 119 5 Metalloporphyrins as Catalysts for Carbene Transfer 121 5.1 Cyclopropanation 121 5.2 Insertion 124 5.3 Sigmatropic Rearrangements 125 5.4 Other Reactions 126 6 Perspectives: Bioorganometallic Catalysis with Artificial Heme Proteins 127 References 127 Organometallic Receptors for Biologically Interesting Molecules 134 1 Introduction 134 2 Trinuclear, Metallamacrocyclic Hosts 135 2.1 Syntheses and Structures of the Hosts 135 2.2 Molecular Recognition of Amino Acids and Peptides 138 2.3 Selective Recognition and Sensing of Lithium Ions 140 2.4 Selective Recognition and Sensing of Fluoride Ions 144 3 Indicator Displacement Assays with an Organometallic Complex 146 3.1 General Principle 146 3.2 A Chemosensor for Histidine- and Methionine-Containing Peptides 146 4 Summary and Outlook 150 References 151 Ferrocene–Peptide Bioconjugates 154 1 Introduction 155 2 Design of Ferrocene–Peptide Bioconjugates 156 2.1 Hydrogen Bonding Properties of 1,1'-Disubstituted Ferrocene-Peptide Bioconjugates 157 2.2 Hydrogen Bonding Properties of Monosubstituted Ferrocene–Peptide Bioconjugates 166 2.3 Transition Metal Complexes of Ferrocene–Peptide Bioconjugates 171 3 Applications of Ferrocene–Peptide Bioconjugates 175 3.1 Ferrocene–Peptide Bioconjugates for Molecular Receptors 176 3.2 Ferrocene–Peptide Bioconjugates for Biomaterials 180 4 Conclusion 182 References 183 Medicinal Properties of Organometallic Compounds 188 1 Introduction 188 2 Cisplatin and Beyond 189 3 Organometallic Pharmaceuticals 193 3.1 Overcoming Drug Resistance 194 3.2 Drug Targeting 198 3.3 Ligand Substitutions 204 4 Drug Cross Reactivity 210 5 Imaging and Diagnosis 213 6 Concluding Remarks 214 References 214 Author Index Volumes 1–17 222 Subject Index (with page links) 230 Back Page 234 Biological Organometallic Chemistry Of B12 / P.a. Butler, B. Kräutler -- Catalytic Nickel-iron-sulfur Clusters: From Minerals To Enzymes / A. Volbeda, J.c. Fontecilla-camps -- Carbene Complexes Of Heme Proteins And Iron Porphyrin Models / G. Simonneaux, P. Le Maux -- Organometallic Receptors For Biologically Interesting Molecules / K. Severin -- Ferrocene-peptide Bioconjugates / T. Moriuchi, T. Hirao -- Medicinal Properties Of Organometallic Compounds / C.s. Allardyce, P.j. Dyson. Volume Editor: Gérard Simonneaux ; With Contributions By C.s. Allardyce ... [et Al.]. Includes Bibliographical References And Indexes. Bioorganometallic Chemistry Has Become A Mature Area Of Science And Is Comprehensively Covered By Leading Experts In This Book. Research In This Rapidly Developing Transdisciplinary Field Is Having Profound Influence On Other Areas Of Scientific Investigation, Ranging From Catalytic Organic Synthesis To Biology, Medicine And Material Science. This Book Provides A Balanced View Of This Rapidly Developing And Promising Subject. Biological Organometallic Chemistry of B 12 ....Pages 1-55 Catalytic Nickel–Iron–Sulfur Clusters: From Minerals to Enzymes....Pages 57-82 Carbene Complexes of Heme Proteins and Iron Porphyrin Models....Pages 83-122 Organometallic Receptors for Biologically Interesting Molecules....Pages 123-142 Ferrocene–Peptide Bioconjugates....Pages 143-175 Medicinal Properties of Organometallic Compounds....Pages 177-210