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An indispensable reference on early main group metals in catalysis for synthetic chemists in academia and industry

Early Main Group Metal Catalysis 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 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 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, natural products chemists, and chemists in industry and academica
 
With contributions from leaders in the field , Early Main Group Metal Catalysis is a valuable guide on the most recent developments and new possibilities of early main group metals in catalysis.

Early Main Group Metal Catalysis

Preface xiii





1 Introduction to Early Main Group Organometallic Chemistry and Catalysis 1

Sjoerd 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 31

Sjoerd 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 59

Sebastian 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 93

Yann Sarazin and Jean-Francois 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 123

Sven 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 151

Sjoerd 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 175

Heiko 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 201

Aaron 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 225

Merle 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 251

Philipp 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 279

Marian Rauser, Sebastian Schroeder, 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 Bronsted 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 311

Yasuhiro 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 347

Michael 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