Note: Cover -- Title Page -- Copyright -- Contents -- Preface -- Chapter 1 Introduction to Early Main Group Organometallic Chemistry and Catalysis -- 1.1 Introduction -- 1.2 s‐Block Organometallics -- 1.2.1 Short History -- 1.2.2 Synthesis of Group 1 Organometallics -- 1.2.3 Synthesis of Group 2 Organometallics -- 1.2.4 Bonding and Structures of s‐Block Organometallics -- 1.2.5 Dynamics of s‐Block Organometallics in Solution -- 1.2.6 Low‐Valent s‐Block Chemistry -- 1.3 s‐Block Organometallics in Catalysis -- 1.3.1 Working Principles in Lewis Acid Catalysis -- 1.3.2 Working Principles in s‐Block Organometallic Catalysis -- 1.3.3 Substrate Activation by s‐Block Metals -- 1.3.4 Future of Early Main Group Metal Catalysis -- List of Abbreviations -- References -- Chapter 2 Polymerization of Alkenes and Polar Monomers by Early Main Group Metal Complexes -- 2.1 Introduction -- 2.2 Alkene Polymerization -- 2.2.1 Styrene Polymerization -- 2.2.2 Polymerization of Modified Styrene -- 2.2.3 Polymerization of Butadiene or Isoprene -- 2.3 Polymerization of Polar Monomers -- 2.3.1 Polymerization of Lactides -- 2.3.2 Copolymerization of Epoxides and CO2 -- 2.4 Conclusions -- List of Abbreviations -- References -- Chapter 3 Intramolecular Hydroamination of Alkenes -- 3.1 Introduction -- 3.2 Hydroamination -- 3.2.1 Scope -- 3.3 s‐Block Metal Catalysis -- 3.3.1 General Remarks -- 3.3.2 Mechanistic Aspects -- 3.3.3 Group 1‐Based Catalysis -- 3.3.3.1 Concerted Reaction -- 3.3.3.2 Radical‐Mediated Intramolecular Hydroamination -- 3.3.3.3 Reactions of N‐Arylhydrazones and Ketoximes -- 3.3.4 Group 2 Metal‐Mediated Catalysis -- 3.3.5 Group 2‐Mediated Asymmetric Cyclohydroamination -- 3.3.6 Lewis Acidic Metal Cation Catalysis -- 3.3.7 Miscellaneous -- 3.4 Outlook -- Acknowledgments -- List of Abbreviations -- References. , Chapter 4 Molecular s‐Block Catalysts for Alkene Hydrophosphination and Related Reactions -- 4.1 Introduction -- 4.2 General Considerations -- 4.3 Hydrophosphination of Alkenes -- 4.3.1 Precatalysts with Nitrogen‐Based Ligands -- 4.3.2 Precatalysts with Oxygen‐Based Ligands -- 4.4 Hydrophosphination of Carbodiimides -- 4.5 Miscellaneous Reactions -- 4.5.1 Hydrophosphinylation of Alkenes and Enones -- 4.5.2 Hydrophosphonylation of Aldehydes and Ketones -- 4.6 Summary and Conclusions -- List of Abbreviations -- References -- Chapter 5 H-N and H-P Bond Addition to Alkynes and Heterocumulenes -- 5.1 Introduction -- 5.2 Hydroamination -- 5.2.1 Hydroamination with Secondary Amines -- 5.2.2 Hydroamination with Primary Amines -- 5.2.3 Proposed Mechanisms for the Hydroamination of Butadiynes -- 5.3 Hydrophosphanylation (Hydrophosphination) -- 5.4 Hydrophosphorylation and Hydrophosphonylation -- 5.5 Summary and Conclusions -- 5.6 Acknowledgments -- 5.7 Abbreviations -- References -- Chapter 6 Early Main Group Metal‐Catalyzed Hydrosilylation of Unsaturated Bonds -- 6.1 Introduction -- 6.2 Historical Development -- 6.3 Nonprecious Metal Hydrosilylation Catalysts -- 6.4 C=C Bond Hydrosilylation with s‐Block Metal Catalysts -- 6.5 C=O Bond Hydrosilylation with s‐Block Metal Catalysts -- 6.6 C=N Bond Hydrosilylation with s‐Block Metal Catalysts -- 6.7 Conclusions -- References -- Chapter 7 Early Main Group Metal Catalyzed Hydrogenation -- 7.1 Introduction -- 7.2 Hydrogenation of C=C Double Bonds -- 7.3 Hydrogenation of C=N Double Bonds -- 7.4 Hydrogenation of C=O Double Bonds -- 7.5 Summary and Perspectives -- References -- Chapter 8 Alkali and Alkaline Earth Element‐Catalyzed Hydroboration Reactions -- 8.1 Introduction and Overview -- 8.2 Thermodynamic Considerations -- 8.2.1 Hydroboration, Hydrosilylation, and Hydrogenation. , 8.2.2 Thermochemistry of Metal-Oxygen Bonds and Element-Hydrogen Bonds -- 8.3 Group 1‐Catalyzed Hydroboration Reactions -- 8.3.1 Overview -- 8.3.2 Base‐Catalyzed Hydroborations -- 8.3.3 Alkali Metal Hydridoborate and Aluminate‐Catalyzed Hydroboration -- 8.4 Group 2‐Catalyzed Hydroboration Reactions -- 8.4.1 Overview -- 8.4.2 -Diketiminate Magnesium-Catalyzed Hydroborations -- 8.4.3 Tris(4,4‐dimethyl‐2‐oxazolinyl)phenylborato Magnesium‐Catalyzed Hydroboration of Ester and Amides -- 8.4.4 Magnesium Triphenylborate‐Catalyzed Hydroboration -- 8.4.5 Supported Catalysts for Hydroboration -- 8.5 Summary and Conclusions -- References -- Chapter 9 Dehydrocoupling and Other Cross‐couplings -- 9.1 Introduction -- 9.2 Early Main Group‐Catalyzed Cross‐DHC of Amines and Boranes -- 9.2.1 Early Stoichiometric Studies with s‐Block Elements -- 9.2.2 s‐Block‐Catalyzed Cross‐dehydrogenative Synthesis of Diaminoboranes -- 9.2.3 s‐Block‐Catalyzed DHC of DMAB -- 9.2.4 Calcium‐Catalyzed Dehydrocoupling of tert‐Butylamine Borane -- 9.2.5 s‐Block‐Catalyzed DHC of Amines and Monohydroboranes -- 9.3 s‐Block‐Catalyzed Cross‐DHC of Amines and Silanes -- 9.3.1 Influence of Precatalysts and Substrates on Reactivity and Selectivity -- 9.3.2 Mechanistic and Computational Analysis -- 9.3.3 Application to the Synthesis of Oligo‐ and Polysilazanes -- 9.4 Other s‐Block‐Catalyzed Cross‐DHC Reactions -- 9.4.1 Alkali Metal‐Catalyzed DHC of Si-H and O-H Bonds -- 9.4.2 s‐Block‐Catalyzed DHC of Si-H and C-H Bonds -- 9.5 Early Main Group‐Mediated Nondehydrogenative Cross‐couplings -- 9.6 Conclusion and Outlook -- References -- Chapter 10 Enantioselective Catalysis with s‐Block Organometallics -- 10.1 Introduction -- 10.2 Lithium‐Based Catalysts -- 10.2.1 Lithium Catalysts Based on Neutral Chiral Ligands -- 10.2.2 Lithium Catalysts Based on Monoanionic Chiral Ligands. , 10.2.3 Lithium Catalysts Based on Dianionic Chiral Ligands -- 10.3 Potassium‐Based Catalysts -- 10.3.1 Potassium Catalysts Based on Monoanionic Chiral Ligands -- 10.4 Magnesium‐Based Catalysts -- 10.4.1 Magnesium Catalysts Based on Monoanionic Chiral Ligands -- 10.4.2 Magnesium Catalysts Based on Dianionic Chiral Ligands -- 10.5 Calcium‐Based Catalysts -- 10.5.1 Calcium Catalysts Based on Monoanionic Chiral Ligands -- 10.5.2 Calcium Catalysts Based on Dianionic Chiral Ligands -- 10.6 Conclusion and Outlook -- List of Abbreviations -- References -- Chapter 11 Early Main Group Metal Lewis Acid Catalysis -- 11.1 Introduction -- 11.1.1 Lewis Acidity of s‐Block Metal Cations -- 11.1.2 Interactions with More than One Lewis Base -- 11.1.3 Counter Anions -- 11.1.4 Solvation -- 11.1.5 Solubility and Aggregation -- 11.1.6 Water Tolerance -- 11.1.7 Relative Lewis Acid Activity of Alkaline and Alkaline Earth Metals -- 11.1.8 Hidden Brønsted Acid -- 11.2 Polarized Carbon-Heteroatom Double Bonds -- 11.2.1 Carboxylates: Anhydrides and Carbonates -- 11.2.2 Aldehydes, Ketones, and Formates -- 11.2.3 , -Unsaturated Carbonyl Compounds -- 11.2.4 Imines and Enamines -- 11.2.5 Mannich Reactions -- 11.2.6 Oxidation and Reduction -- 11.2.7 Donor-Acceptor Cyclopropanes -- 11.2.8 Diels-Alder Reaction and Cycloaddition -- 11.3 Activation of Polarized Single Bonds -- 11.3.1 Opening of Three‐Membered Heterocycles -- 11.3.2 Leaving Groups -- 11.3.3 Ca2+‐Catalyzed Dehydroxylation as a Special Case -- 11.4 Activation of Unpolarized Double Bonds -- 11.5 Summary and Conclusions -- References -- Chapter 12 Enantioselective Group 2 Metal Lewis Acid Catalysis -- 12.1 Introduction -- 12.2 Catalytic Enantioselective Reactions Using Chiral Magnesium Complexes -- 12.2.1 Chiral Magnesium‐Catalyzed Diels-Alder and 1,3‐Dipolar Cycloaddition Reactions. , 12.2.2 Chiral Magnesium‐Catalyzed 1,4‐Addition Reactions -- 12.2.3 Chiral Magnesium‐Catalyzed Addition Reactions to Carbonyl Compounds -- 12.2.4 Chiral Magnesium‐Catalyzed Addition Reactions with Imines -- 12.2.5 Chiral Magnesium‐Catalyzed Ring‐Opening Reactions of Epoxide and Aziridine -- 12.2.6 Chiral Magnesium-Catalyzed -Functionalization Reactionsof Carbonyl Compounds -- 12.2.7 Various Chiral Magnesium‐Catalyzed Reactions -- 12.3 Catalytic Enantioselective Reactions Using Chiral Calcium Complexes -- 12.3.1 Chiral Calcium‐Catalyzed Addition Reactions to Carbonyl Compounds -- 12.3.2 Chiral Calcium‐Catalyzed 1,4‐Addition Reactions -- 12.3.3 Chiral Calcium‐Catalyzed Addition Reactions with Imines -- 12.3.4 Chiral Calcium-Catalyzed -Functionalization Reactionswith Carbonyl Compounds -- 12.3.5 Chiral Calcium‐Catalyzed Cycloaddition Reactions -- 12.3.6 Chiral Calcium‐Catalyzed Hydroamination Reactions -- 12.3.7 Chiral Calcium‐Catalyzed Epoxidation Reactions -- 12.3.8 Chiral Calcium‐Catalyzed Aziridine Ring‐Opening Reaction -- 12.4 Catalytic Enantioselective Reactions Using Chiral Strontium Complexes -- 12.4.1 Chiral Strontium‐Catalyzed 1,4‐Addition Reactions -- 12.4.2 Chiral Strontium‐Catalyzed Addition Reactions with Imines -- 12.4.3 Chiral Strontium‐Catalyzed Oxime Formation -- 12.5 Catalytic Enantioselective Reactions Using Chiral Barium Complexes -- 12.5.1 Chiral Barium‐Catalyzed Addition Reactions to Carbonyl Compounds and Imines -- 12.5.2 Chiral Barium‐Catalyzed 1,4‐Addition Reactions -- 12.5.3 Chiral Barium‐Catalyzed Diels-Alder Reactions -- 12.6 Summary and Outlook -- References -- Chapter 13 Miscellaneous Reactions -- 13.1 Introduction -- 13.2 Privileged Substrates and s‐Block Reactivity -- 13.3 Reactivity with Multiply Bonded Substrates -- 13.3.1 Tishchenko Dimerization of Aldehydes -- 13.3.2 Trimerization of Organic Isocyanates. , 13.3.3 Hydroalkoxylation of Alkynyl Alcohols.