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Early Main Group Metal Catalysis


Early Main Group Metal Catalysis

Concepts and Reactions
1. Aufl.

von: Sjoerd Harder

133,99 €

Verlag: Wiley-VCH
Format: EPUB
Veröffentl.: 22.11.2019
ISBN/EAN: 9783527818037
Sprache: englisch
Anzahl Seiten: 144

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Beschreibungen

Early Main Group Metal Catalysis gives a comprehensive overview of catalytic reactions in the presence of group 1 and group 2 metals. Chapters are ordered to reaction type, contain educational elements and deal with concepts illustrated by examples that cover the main developments. After a short introduction on polar organometallic chemistry and synthesis of early main group metal complexes, a variety of catalytic reactions are described, e.g. polymerization of alkenes, hydroamination and phosphination reactions, hydrosilylation, hydroboration and hydrogenation catalysis, as well as enantioselective and Lewis-acid catalysis. The book addresses organic chemists and researchers in industry interested in the state-of-the-art and new possibilities of early main group metal catalysis as well as newcomers to the field. Written by a team of leaders in the field, it is a very welcome addition to the area of main group metal chemistry, and to the field of catalysis.
Preface xiii 1 Introduction to Early Main Group Organometallic Chemistry and Catalysis 1Sjoerd Harder 1.1 Introduction 1 1.2 s-Block Organometallics 1 1.2.1 Short History 1 1.2.2 Synthesis of Group 1 Organometallics 2 1.2.3 Synthesis of Group 2 Organometallics 4 1.2.4 Bonding and Structures of s-Block Organometallics 8 1.2.5 Dynamics of s-Block Organometallics in Solution 13 1.2.6 Low-Valent s-Block Chemistry 16 1.3 s-Block Organometallics in Catalysis 17 1.3.1 Working Principles in Lewis Acid Catalysis 17 1.3.2 Working Principles in s-Block Organometallic Catalysis 19 1.3.3 Substrate Activation by s-Block Metals 21 1.3.4 Future of Early Main Group Metal Catalysis 23 List of Abbreviations 24 References 24 2 Polymerization of Alkenes and Polar Monomers by Early Main Group Metal Complexes 31Sjoerd Harder 2.1 Introduction 31 2.2 Alkene Polymerization 32 2.2.1 Styrene Polymerization 33 2.2.2 Polymerization of Modified Styrene 40 2.2.3 Polymerization of Butadiene or Isoprene 43 2.3 Polymerization of Polar Monomers 45 2.3.1 Polymerization of Lactides 45 2.3.2 Copolymerization of Epoxides and CO2 50 2.4 Conclusions 53 List of Abbreviations 54 References 54 3 Intramolecular Hydroamination of Alkenes 59Sebastian Bestgen and Peter W. Roesky 3.1 Introduction 59 3.2 Hydroamination 60 3.2.1 Scope 62 3.3 s-Block Metal Catalysis 64 3.3.1 General Remarks 64 3.3.2 Mechanistic Aspects 65 3.3.3 Group 1-Based Catalysis 68 3.3.3.1 Concerted Reaction 68 3.3.3.2 Radical-Mediated Intramolecular Hydroamination 71 3.3.3.3 Reactions of N-Arylhydrazones and Ketoximes 72 3.3.4 Group 2 Metal-Mediated Catalysis 74 3.3.5 Group 2-Mediated Asymmetric Cyclohydroamination 83 3.3.6 Lewis Acidic Metal Cation Catalysis 84 3.3.7 Miscellaneous 85 3.4 Outlook 86 Acknowledgments 87 List of Abbreviations 87 References 88 4 Molecular s-Block Catalysts for Alkene Hydrophosphination and Related Reactions 93Yann Sarazin and Jean-François Carpentier 4.1 Introduction 93 4.2 General Considerations 95 4.3 Hydrophosphination of Alkenes 96 4.3.1 Precatalysts with Nitrogen-Based Ligands 97 4.3.2 Precatalysts with Oxygen-Based Ligands 110 4.4 Hydrophosphination of Carbodiimides 112 4.5 Miscellaneous Reactions 114 4.5.1 Hydrophosphinylation of Alkenes and Enones 114 4.5.2 Hydrophosphonylation of Aldehydes and Ketones 116 4.6 Summary and Conclusions 117 List of Abbreviations 118 References 118 5 H—Nand H—P Bond Addition to Alkynes and Heterocumulenes 123Sven Krieck and Matthias Westerhausen 5.1 Introduction 123 5.2 Hydroamination 124 5.2.1 Hydroamination with Secondary Amines 125 5.2.2 Hydroamination with Primary Amines 128 5.2.3 Proposed Mechanisms for the Hydroamination of Butadiynes 130 5.3 Hydrophosphanylation (Hydrophosphination) 134 5.4 Hydrophosphorylation and Hydrophosphonylation 138 5.5 Summary and Conclusions 143 5.6 Acknowledgments 146 5.7 Abbreviations 146 References 146 6 Early Main Group Metal-Catalyzed Hydrosilylation of Unsaturated Bonds 151Sjoerd Harder 6.1 Introduction 151 6.2 Historical Development 151 6.3 Nonprecious Metal Hydrosilylation Catalysts 153 6.4 C=C Bond Hydrosilylation with s-Block Metal Catalysts 155 6.5 C=O Bond Hydrosilylation with s-Block Metal Catalysts 161 6.6 C=N Bond Hydrosilylation with s-Block Metal Catalysts 167 6.7 Conclusions 170 References 171 7 Early Main Group Metal Catalyzed Hydrogenation 175Heiko Bauer and Sjoerd Harder 7.1 Introduction 175 7.2 Hydrogenation of C=C Double Bonds 178 7.3 Hydrogenation of C=N Double Bonds 187 7.4 Hydrogenation of C=O Double Bonds 191 7.5 Summary and Perspectives 194 References 197 8 Alkali and Alkaline Earth Element-Catalyzed Hydroboration Reactions 201Aaron D. Sadow 8.1 Introduction and Overview 201 8.2 Thermodynamic Considerations 203 8.2.1 Hydroboration, Hydrosilylation, and Hydrogenation 203 8.2.2 Thermochemistry of Metal–Oxygen Bonds and Element–Hydrogen Bonds 205 8.3 Group 1-Catalyzed Hydroboration Reactions 207 8.3.1 Overview 207 8.3.2 Base-Catalyzed Hydroborations 207 8.3.3 Alkali Metal Hydridoborate and Aluminate-Catalyzed Hydroboration 210 8.4 Group 2-Catalyzed Hydroboration Reactions 214 8.4.1 Overview 214 8.4.2 ?-Diketiminate Magnesium-Catalyzed Hydroborations 215 8.4.3 Tris(4,4-dimethyl-2-oxazolinyl)phenylborato Magnesium-Catalyzed Hydroboration of Ester and Amides 217 8.4.4 Magnesium Triphenylborate-Catalyzed Hydroboration 221 8.4.5 Supported Catalysts for Hydroboration 221 8.5 Summary and Conclusions 222 References 222 9 Dehydrocoupling and Other Cross-couplings 225Merle Arrowsmith 9.1 Introduction 225 9.2 Early Main Group-Catalyzed Cross-DHC of Amines and Boranes 228 9.2.1 Early Stoichiometric Studies with s-Block Elements 228 9.2.2 s-Block-Catalyzed Cross-dehydrogenative Synthesis of Diaminoboranes 229 9.2.3 s-Block-Catalyzed DHC of DMAB 231 9.2.4 Calcium-Catalyzed Dehydrocoupling of tert-Butylamine Borane 235 9.2.5 s-Block-Catalyzed DHC of Amines and Monohydroboranes 235 9.3 s-Block-Catalyzed Cross-DHC of Amines and Silanes 238 9.3.1 Influence of Precatalysts and Substrates on Reactivity and Selectivity 238 9.3.2 Mechanistic and Computational Analysis 240 9.3.3 Application to the Synthesis of Oligo- and Polysilazanes 242 9.4 Other s-Block-Catalyzed Cross-DHC Reactions 243 9.4.1 Alkali Metal-Catalyzed DHC of Si—H and O—H Bonds 243 9.4.2 s-Block-Catalyzed DHC of Si—H and C—H Bonds 243 9.5 Early Main Group-Mediated Nondehydrogenative Cross-couplings 244 9.6 Conclusion and Outlook 245 References 246 10 Enantioselective Catalysis with s-Block Organometallics 251Philipp Stegner and Sjoerd Harder 10.1 Introduction 251 10.2 Lithium-Based Catalysts 252 10.2.1 Lithium Catalysts Based on Neutral Chiral Ligands 252 10.2.2 Lithium Catalysts Based on Monoanionic Chiral Ligands 255 10.2.3 Lithium Catalysts Based on Dianionic Chiral Ligands 257 10.3 Potassium-Based Catalysts 259 10.3.1 Potassium Catalysts Based on Monoanionic Chiral Ligands 260 10.4 Magnesium-Based Catalysts 262 10.4.1 Magnesium Catalysts Based on Monoanionic Chiral Ligands 263 10.4.2 Magnesium Catalysts Based on Dianionic Chiral Ligands 266 10.5 Calcium-Based Catalysts 269 10.5.1 Calcium Catalysts Based on Monoanionic Chiral Ligands 269 10.5.2 Calcium Catalysts Based on Dianionic Chiral Ligands 273 10.6 Conclusion and Outlook 275 List of Abbreviations 275 References 276 11 Early Main Group Metal Lewis Acid Catalysis 279Marian Rauser, Sebastian Schröder, and Meike Niggemann 11.1 Introduction 279 11.1.1 Lewis Acidity of s-Block Metal Cations 280 11.1.2 Interactions with More than One Lewis Base 281 11.1.3 Counter Anions 282 11.1.4 Solvation 283 11.1.5 Solubility and Aggregation 283 11.1.6 Water Tolerance 284 11.1.7 Relative Lewis Acid Activity of Alkaline and Alkaline Earth Metals 285 11.1.8 Hidden Brønsted Acid 287 11.2 Polarized Carbon–Heteroatom Double Bonds 287 11.2.1 Carboxylates: Anhydrides and Carbonates 288 11.2.2 Aldehydes, Ketones, and Formates 289 11.2.3 ?,?-Unsaturated Carbonyl Compounds 291 11.2.4 Imines and Enamines 292 11.2.5 Mannich Reactions 294 11.2.6 Oxidation and Reduction 294 11.2.7 Donor–Acceptor Cyclopropanes 294 11.2.8 Diels–Alder Reaction and Cycloaddition 295 11.3 Activation of Polarized Single Bonds 296 11.3.1 Opening of Three-Membered Heterocycles 296 11.3.2 Leaving Groups 297 11.3.3 Ca2+-Catalyzed Dehydroxylation as a Special Case 299 11.4 Activation of Unpolarized Double Bonds 305 11.5 Summary and Conclusions 307 References 307 12 Enantioselective Group 2Metal Lewis Acid Catalysis 311Yasuhiro Yamashita, Tetsu Tsubogo, and Sh? Kobayashi 12.1 Introduction 311 12.2 Catalytic Enantioselective Reactions Using Chiral Magnesium Complexes 313 12.2.1 Chiral Magnesium-Catalyzed Diels–Alder and 1,3-Dipolar Cycloaddition Reactions 313 12.2.2 Chiral Magnesium-Catalyzed 1,4-Addition Reactions 315 12.2.3 Chiral Magnesium-Catalyzed Addition Reactions to Carbonyl Compounds 318 12.2.4 Chiral Magnesium-Catalyzed Addition Reactions with Imines 319 12.2.5 Chiral Magnesium-Catalyzed Ring-Opening Reactions of Epoxide and Aziridine 321 12.2.6 Chiral Magnesium-Catalyzed ?-Functionalization Reactions of Carbonyl Compounds 323 12.2.7 Various Chiral Magnesium-Catalyzed Reactions 324 12.3 Catalytic Enantioselective Reactions Using Chiral Calcium Complexes 324 12.3.1 Chiral Calcium-Catalyzed Addition Reactions to Carbonyl Compounds 324 12.3.2 Chiral Calcium-Catalyzed 1,4-Addition Reactions 326 12.3.3 Chiral Calcium-Catalyzed Addition Reactions with Imines 331 12.3.4 Chiral Calcium-Catalyzed ?-Functionalization Reactions with Carbonyl Compounds 333 12.3.5 Chiral Calcium-Catalyzed Cycloaddition Reactions 334 12.3.6 Chiral Calcium-Catalyzed Hydroamination Reactions 334 12.3.7 Chiral Calcium-Catalyzed Epoxidation Reactions 336 12.3.8 Chiral Calcium-Catalyzed Aziridine Ring-Opening Reaction 337 12.4 Catalytic Enantioselective Reactions Using Chiral Strontium Complexes 337 12.4.1 Chiral Strontium-Catalyzed 1,4-Addition Reactions 337 12.4.2 Chiral Strontium-Catalyzed Addition Reactions with Imines 338 12.4.3 Chiral Strontium-Catalyzed Oxime Formation 339 12.5 Catalytic Enantioselective Reactions Using Chiral Barium Complexes 339 12.5.1 Chiral Barium-Catalyzed Addition Reactions to Carbonyl Compounds and Imines 339 12.5.2 Chiral Barium-Catalyzed 1,4-Addition Reactions 340 12.5.3 Chiral Barium-Catalyzed Diels–Alder Reactions 341 12.6 Summary and Outlook 341 References 342 13 Miscellaneous Reactions 347Michael S. Hill 13.1 Introduction 347 13.2 Privileged Substrates and s-Block Reactivity 347 13.3 Reactivity with Multiply Bonded Substrates 351 13.3.1 Tishchenko Dimerization of Aldehydes 351 13.3.2 Trimerization of Organic Isocyanates 352 13.3.3 Hydroalkoxylation of Alkynyl Alcohols 353 13.3.4 Catalytic Isomerization and C–C Coupling with Terminal Alkynes 354 13.3.5 Activation and Deoxygenation of C—O Multiple Bonds 358 13.4 Single-Electron Transfer Steps in s-Block-Centered Catalysis 361 13.5 “Beyond” Hydrofunctionalization and Dehydrocoupling 363 13.6 Conclusions and Conjecture 365 References 367 Index 373
Sjoerd Harder holds the Chair of Inorganic and Organometallic Chemistry at the University of Erlangen-Nuremberg, Germany. He has authored over 175 scientific publications, mainly on the topic of early main group metal chemistry and is considered a pioneer in heavier alkaline-earth metal chemistry and group 2 metal applications in catalysis.
An indispensable reference on early main group metals in catalysis for synthetic chemists in academia and industry Early Main Group Metal Catalysis: Concepts and Reactions contains a comprehensive overview of catalytic reactions in the presence of group 1 and group 2 metals. The book's chapters are organized according to the type of reaction to help easily navigate information. Every chapter contains basic information as well as a short educational background on the elements covered, and fundamental concepts are enhanced with illustrative examples that cover the main developments. The text describes various reactions including: polymerization of alkenes, hydroamination and phosphination reactions, hydrosilylation, hydroboration and hydrogenation catalysis, and enantioselective and Lewis acid catalysis. This important book: Provides a short introduction on polar organometallic chemistry and synthesis of early main group metal complexes Reviews the chemistry of the early main group metals, such as calcium and magnesium, that are useful catalysts for various organic transformations Addresses catalytic chemists, chemists working with organometallics, organic chemists, and natural products chemists as well in industry as in academia. With contributions from leaders in the field, Early Main Group Metal Catalysis: Concepts and Reactions is a valuable guide on the most recent developments and new possibilities of early main group metals in catalysis.

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