Iron Catalysis in Organic Chemistry Reactions and Applications

by Plietker, Bernd

• ISBN13: 9783527319275
• ISBN10: 3527319271
• Edition: 1st
• Format: Hardcover
• Copyright: 2008-09-22
• Publisher: Wiley-VCH

Summary

This first comprehensive book to cover this exciting field also deals with the biological aspects, such as enzymes with iron.Following an introduction, this handy reference and handbook goes on to deal with reductions, oxidations of C, H- and C=C bonds, oxidative allylic oxygenation and amination, the oxidation of heteroatoms, cross coupling reactions, aromatic and nucleophilic substitutions, addition to carbonyl compounds, and cyclisations as well as ring opening reactions.The chapters are clearly classified according to the reaction type, allowing readers to quickly locate the desired information.

Author Biography

Bernd Plietker, born in Gronau (Germany) in 1971, studied chemistry in M++nster and Dresden. In 1999 he received his PhD under the guidance of Peter Metz at the University of Dresden. After postdoctoral stays in the group of Jan-Erling B+ñckvall (Stockholm) and Barry Trost (Stanford) he began his independent research career associated with Norbert Krause (Dortmund). In 2007 he became a Professor of Organic Chemistry at the University of Stuttgart. His research interests include the development of sustainable metal catalysis (based on ruthenium or iron complexes) and their application in the total synthesis of natural products or natural product like libraries.

He has received a Liebig fellowship and the Award of the Otto-Roehm Gedaechtnisstiftung.

Table of Contents

Preface	p. XI
List of Contributors	p. XIII
Iron Complexes in Organic Chemistry	p. 1
Introduction	p. 1
General Aspects of Iron Complex Chemistry	p. 2
Electronic Configuration, Oxidation States, Structures	p. 2
Fundamental Reactions	p. 2
Organoiron Complexes and Their Applications	p. 4
Binary Carbonyl-Iron Complexes	p. 5
Alkene-Iron Complexes	p. 7
Allyl- and Trimethylenemethane-Iron Complexes	p. 8
Acyl- and Carbene-Iron Complexes	p. 9
Diene-Iron Complexes	p. 11
Ferrocenes	p. 18
Arene-Iron Complexes	p. 18
Catalysis Using Iron Complexes	p. 20
Iron Complexes as Substrates and/or Products in Catalytic Reactions	p. 20
Iron Complexes as Ligands for Other Transition Metal Catalysts	p. 21
Iron Complexes as Catalytically Active Species	p. 21
References	p. 24
Iron Catalysis in Biological and Biomimetic Reactions	p. 29
Non-heme Iron Catalysts in Biological and Biomimetic Transformations	p. 29
Introduction: Iron in Biological Processes	p. 29
Non-heme Iron Proteins	p. 30
Mononuclear Iron Sites	p. 30
Dinuclear Iron Sites	p. 39
Summary	p. 45
References	p. 46
Organic Reactions Catalyzed by Heme Proteins	p. 48
Classification and General Reactivity Schemes of Heme Proteins Used in Organic Synthesis	p. 48
Organic Reactions Catalyzed by Cytochromes P450	p. 51
Organic Reactions Catalyzed by Heme Peroxidases	p. 56
Dehydrogenations ("Peroxidase Reactivity")	p. 56
Sulfoxidations ("Peroxygenase Reactivity")	p. 57
Peroxide Disproportionation ("Catalase Reactivity")	p. 58
Halogenation ("Haloperoxidase Reactivity")	p. 61
Epoxidations ("Monoxygenase Activity")	p. 62
References	p. 66
Iron-catalyzed Oxidation Reactions	p. 73
Oxidations of C-H and C=C Bonds	p. 73
Gif Chemistry	p. 73
Alkene Epoxidation	p. 80
Alkene Dihydroxylation	p. 82
The Kharasch Reaction and Related Reactions	p. 84
Aziridination and Diamination	p. 87
References	p. 89
Oxidative Allylic Oxygenation and Amination	p. 92
Introduction	p. 92
Iron-catalyzed Allylic Oxidations	p. 93
Simple Iron Salts	p. 93
Fe(III) Complexes with Bidentate Ligands	p. 94
Fe[superscript 3+]/Fe[superscript 2+] Porphyrin and Phthalocyanine Complexes	p. 95
Iron(III) Salen Complexes	p. 100
Non-heme Iron Complexes with Tetra- and Pentadentate Ligands	p. 100
Oxidative Allylic Aminations	p. 103
Conclusion	p. 107
References	p. 107
Oxidation of Heteroatoms (N and S)	p. 109
Oxidation of Nitrogen Compounds	p. 109
Oxidation of Hydroxylamines to Nitroso Compounds	p. 109
Oxidation of Arylamines	p. 110
Other N-Oxidations	p. 110
Oxidation of Sulfur Compounds	p. 111
Oxidation of Thiols to Disulfides	p. 111
Oxidation of Sulfides	p. 113
Oxidative Imination of Sulfur Compounds	p. 119
References	p. 122
Reduction of Unsaturated Compounds with Homogeneous Iron Catalysts	p. 125
Introduction	p. 125
Hydrogenation of Carbonyl Compounds	p. 125
Hydrogenation of Carbon-Carbon Double Bonds	p. 129
Hydrogenation of Imines and Similar Compounds	p. 136
Catalytic Hydrosilylations	p. 136
Conclusion	p. 141
References	p. 142
Iron-catalyzed Cross-coupling Reactions	p. 147
Introduction	p. 147
Cross-coupling Reactions of Alkenyl Electrophiles	p. 147
Cross-coupling Reactions of Aryl Electrophiles	p. 154
Cross-coupling Reactions of Alkyl Electrophiles	p. 161
Cross-coupling Reactions of Acyl Electrophiles	p. 168
Iron-catalyzed Carbometallation Reactions	p. 170
Conclusion	p. 172
References	p. 173
Iron-catalyzed Aromatic Substitutions	p. 177
General Aspects	p. 177
Electrophilic Aromatic Substitutions	p. 178
Halogenation Reactions	p. 178
Nitration Reactions	p. 179
Sulfonylation Reactions	p. 180
Friedel-Crafts Acylations	p. 181
Friedel-Crafts Alkylations	p. 183
Alkylation with Alcohols, Ethers and Esters	p. 184
Alkylation with Alkenes	p. 186
Nucleophilic Aromatic Substitutions	p. 188
References	p. 191
Iron-catalyzed Substitution Reactions	p. 197
Introduction	p. 197
Iron-catalyzed Nucleophilic Substitutions	p. 197
Nucleophilic Substitutions of Non-activated C-X Bonds	p. 197
Introduction	p. 197
Nucleophilic Substitutions Using Lewis Acidic Fe Catalysts	p. 198
Substitutions Catalyzed by Ferrate Complexes	p. 199
Nucleophilic Substitution of Allylic and Propargylic C-X Bonds	p. 202
Reactions Catalyzed by Lewis Acidic Fe Salts	p. 202
Nucleophilic Substitutions Involving Ferrates	p. 205
Conclusion	p. 213
References	p. 214
Addition and Conjugate Addition Reactions to Carbonyl Compounds	p. 217
Introduction	p. 217
Additions to Aldehydes and Ketones	p. 218
Oxygen Nucleophiles	p. 218
Carbon Nucleophiles	p. 219
Additions to Imines and Iminium Ions	p. 223
Additions to Carboxylic Acids and Their Derivatives	p. 224
Oxygen Nucleophiles	p. 224
Carbon Nucleophiles	p. 225
Conjugate Addition to [alpha],[beta]-Unsaturated Carbonyl Compounds	p. 226
Carbon Nucleophiles	p. 226
Michael Reactions	p. 226
Vinylogous Michael Reactions	p. 230
Asymmetric Michael Reactions	p. 232
Michael Reactions in Ionic Liquids and Heterogeneous Catalysis	p. 233
Nitrogen Nucleophiles	p. 235
Synthesis of Heterocycles	p. 236
Pyridine and Quinoline Derivatives	p. 236
Pyrimidine and Pyrazine Derivatives	p. 238
Benzo- and Dibenzopyrans	p. 238
References	p. 239
Iron-catalyzed Cycloadditions and Ring Expansion Reactions	p. 245
Introduction	p. 245
Cycloisomerization and Alder-Ene Reaction	p. 245
[2+1]-Cycloadditions	p. 249
Iron-catalyzed Aziridine Formation	p. 249
Iron-catalyzed Epoxide Formation	p. 251
Iron-catalyzed Cyclopropane Formation	p. 252
[2+2]-Cycloaddition	p. 254
[4+1]-Cycloadditions	p. 256
[4+2]-Cycloadditions	p. 257
Diels-Alder Reactions with Normal Electron Demand	p. 257
Diels-Alder Reactions with Neutral Electron Demand	p. 259
Diels-Alder Reactions with Inverse Electron Demand	p. 260
Cyclotrimerization	p. 260
[3+2]-Cycloadditions	p. 262
[3+3]-Cycloadditions	p. 263
Ring Expansion Reactions	p. 263
Conclusion	p. 266
References	p. 266
Index	p. 271
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