Manganese Catalysis in Organic Synthesis

Description

Manganese Catalysis in Organic Synthesis A must-read reference for anyone interested in catalyst design and sustainable organic synthesis In Manganese Catalysis in Organic Synthesis, distinguished researcher Jean-Baptiste Sortais delivers an insightful and robust overview of the use of manganese in homogenous catalysis. The editor includes papers from authoritative academics describing the organometallic precursors used to develop manganese catalysts and covers critical applications in organic synthesis, including reduction to oxidation reactions, C-C, C-N, C-X bond formation reactions, cross-coupling reactions, C-H bond activation to dihydroxylation and epoxidation reactions. Manganese Catalysis in Organic Synthesis is a practical resource for every organic chemist in academia and industry with an interest in non-noble metal catalysis, organic synthesis, and sustainable chemistry. It is intuitively and clearly organized, covering the most important synthetic procedures using homogenous manganese catalysts. It is also the ideal companion to works like Cobalt Catalysis in Organic Synthesis, Nickel Catalysis in Organic Synthesis, and Iron Complexes in Catalysis. Readers will also enjoy: Thorough introductions to organometallic manganese compounds in organic synthesis and manganese-catalyzed hydrogenation and hydrogen transfer reactionsA comprehensive exploration of manganese-catalyzed hydrogen borrowing reactions and dehydrogenative coupling reactionsPractical discussions of manganese-catalyzed hydrosilylation and hydroboration reactions and manganese-catalyzed electro- and photocatalysis transformationsIn-depth examinations of manganese-catalyzed C-H oxygenation reactions and manganese-catalyzed organometallic C-H activationInsightful treatments of manganese-catalyzed cross-coupling processes and manganese(III) acetate mediated cyclizations Perfect for catalytic, organic, and pharmaceutical chemists, Manganese Catalysis in Organic Synthesis deserves a place in the libraries of researchers and professionals interested in catalyst design and sustainable organic synthesis. Cover Title Page Copyright Contents Preface Chapter 1 Organometallic Manganese Compounds in Organic Synthesis 1.1 Introduction 1.2 Basic Manganese Precursors Relevant to Organometallic Chemistry 1.3 Overview of the Synthetic Chemistry for Main Classes of Mn(I) Complexes 1.4 Planar Chiral Ligands Based on Cymantrene Scaffold 1.5 Mn(I)‐Mediated Transformations in Organic Synthesis 1.5.1 Ring‐Centered Reactivity in Half‐Sandwich Mn(I) π‐Complexes 1.5.2 Preparation of Allenes Using [Cp′(CO)2Mn] Auxiliary 1.5.3 Synthetic Applications of Mn(I) Fischer Carbenes 1.5.4 Carbonyl‐Containing Manganese σ‐Complexes in Organic Synthesis 1.5.5 Mn‐Mediated Synthesis of Organophosphorous Compounds 1.5.6 Backbone Modification of N‐heterocyclic Carbenes in Mn(I) Coordination Sphere 1.6 Summary and Conclusions References Chapter 2 Manganese‐Catalyzed Hydrogenation and Hydrogen Transfer Reactions 2.1 Introduction 2.2 Pincer‐Type Manganese Complexes 2.2.1 PNP Ligands 2.2.1.1 PN‐sp3P Ligand 2.2.1.2 PN‐sp2P Ligand 2.2.2 PNN Ligands 2.2.2.1 PN‐sp3N Ligand 2.2.2.2 PN‐sp2N Ligand 2.2.3 NNN Ligands 2.3 Non‐pincer‐Type Manganese Complexes 2.3.1 NN Ligands 2.3.1.1 N‐sp3,N‐sp3 Ligand 2.3.1.2 N‐sp2,N‐sp2 Ligand 2.3.1.3 N‐sp2,N‐sp3 Ligand 2.3.2 PP Ligands 2.3.3 NP Ligands 2.3.3.1 N‐sp3,P‐sp3 Ligand 2.3.3.2 N‐sp2,P‐sp3 Ligand 2.3.4 CP Ligand 2.3.5 CN Ligand 2.4 Other Manganese Complexes 2.4.1 Monodentate Ligand 2.4.2 Tetradentate Ligand 2.5 Conclusions References Chapter 3 Manganese‐Catalyzed Hydrogen‐Borrowing and Dehydrogenative Coupling Reactions 3.1 Introduction 3.2 Acceptorless Dehydrogenative Coupling (ADC) 3.2.1 Synthesis of Aldimines, Cyclic Imides, and Amides 3.2.2 Synthesis of Esters and Functionalizations of Nitriles and Alkanes 3.2.3 Synthesis and Derivatization of Heterocycles 3.3 Hydrogen‐Borrowing Reactions 3.3.1 Alkylation of Amines 3.3.2 Alkylation of Alcohols and Ketones 3.3.3 Alkylation of Amides and Esters 3.3.4 Alkylation of Nitriles and Sulfonamide 3.3.5 Upgrading of Ethanol into 1‐Butanol 3.3.6 Alkylation of Hydrazine 3.3.7 Combining Acceptorless Dehydrogenative Coupling with Hydrogen‐Borrowing 3.4 Conclusions and Perspectives References Chapter 4 Manganese‐Catalyzed Hydrosilylation and Hydroboration Reactions 4.1 Introduction 4.2 Hydrosilylation 4.2.1 Hydrosilylation of Carbonyls and Carboxylates 4.2.2 Hydrosilylation of Amides 4.2.3 Hydrosilylation of Carbon Dioxide 4.2.4 Hydrosilylation of CC and CC Bonds 4.2.4.1 Olefin Hydrosilylation 4.2.4.2 Alkyne Hydrosilylation 4.3 Hydroboration 4.3.1 Hydroboration of CO Bonds 4.3.2 Hydroboration of Alkenes 4.3.3 Hydroboration of Alkynes 4.3.4 Hydroboration of Nitriles 4.4 Summary and Conclusions References Chapter 5 Manganese Complexes for Electro‐ and Photocatalytic Transformations 5.1 Introduction 5.2 Mn‐Catalyzed Organic Oxidations 5.3 Mn‐Catalyzed Reductions and Other Organic Transformations 5.4 Mn‐Catalyzed CO2 Reduction 5.4.1 Electrocatalytic CO2 Reduction with Manganese‐Based Catalysts 5.4.1.1 Pyridine‐Based Complexes 5.4.1.2 Diimine‐Based Complexes 5.4.1.3 N‐Heterocyclic Carbene‐Based Complexes 5.4.2 Photochemical CO2 Reduction 5.4.3 Heterogenization of Molecular Mn Catalysts for the CO2 Reduction Reaction 5.5 Conclusions References Chapter 6 Manganese‐Catalyzed CH Oxygenation Reactions 6.1 Introduction 6.2 Selective Manganese‐Catalyzed C–H Oxidation Reactions: Early Studies 6.3 Manganese‐Catalyzed Chemo‐ and Regioselective C–H Oxidations with Hydrogen Peroxide 6.4 Manganese‐Catalyzed Enantioselective C–H Oxidations 6.5 Manganese‐Catalyzed Oxidative Desymmetrizations 6.6 Mn‐Catalyzed Oxidative Kinetic Resolution of sec‐Alcohols 6.7 Mn‐Catalyzed Oxidation of Aromatic Compounds 6.8 Summary and Conclusions Acknowledgment References Chapter 7 Manganese‐Catalyzed Organometallic CH Activation 7.1 Introduction 7.2 Stoichiometric Cyclometalation with Manganese Complexes 7.3 Manganese‐Catalyzed CC Bond Formation via Directed CH Activation 7.3.1 Insertion of CC Bonds into Manganacycles 7.3.2 Insertion of CC Bonds into Manganacycles 7.3.3 Insertion of Allene into Manganacycles 7.3.4 Insertion of CX (X = O, N) Bond into Manganacycles 7.3.5 Miscellaneous Reactions Involving C–H Activation 7.4 Summary and Outlook References Chapter 8 Manganese‐Catalyzed Cross‐Coupling Processes 8.1 Introduction 8.2 CC Bond Formation via Mn‐Catalyzed Cross‐Coupling Reactions 8.2.1 Mn‐Catalyzed Kumada Cross‐Coupling Reactions 8.2.1.1 Aryl Halides with Grignard Reagents 8.2.1.2 Heteroaryl Halides with Grignard Reagents 8.2.1.3 Vinyl(Pseudo)Halides with Grignard Reagents 8.2.1.4 Conclusion on Mn‐Catalyzed Kumada Cross‐Coupling Reactions 8.2.2 Mn‐Catalyzed Stille Cross‐Coupling Reactions 8.2.3 Mn‐Catalyzed Coupling Reactions of Organometallic Reagents Under Oxidative Conditions 8.2.3.1 Homocoupling Reactions 8.2.3.2 Heterocoupling Reactions 8.2.4 Mechanistic Insights 8.2.5 Conclusion on Mn‐Catalyzed Coupling Reactions of Organometallic Reagents Under Oxidative Conditions 8.3 Mn‐Catalyzed Carbon–Heteroatom Bond Formation 8.3.1 CN Bond Formation 8.3.2 CO Bond Formation 8.3.3 CS Bond Formation 8.3.4 CB Bond Formation 8.3.5 Conclusion on Mn‐Catalyzed CY Bond Formation 8.4 Summary and Conclusions Acknowledgment References Chapter 9 Manganese(III) Acetate‐Mediated Cyclizations 9.1 Introduction 9.2 Mechanistic Considerations 9.3 Monocyclizations 9.3.1 Radicals Derived from β‐Keto Esters and β‐Diketones that Lead to Cycloalkanones 9.3.2 Radicals Derived from β‐Keto Esters, β‐Diketones, or Malonate Esters that Lead to Cycloalkanes 9.3.3 Formation of Lactones 9.3.4 Formation of Lactams 9.3.5 Cyclizations to Aromatic Rings 9.4 Tandem, Triple, and Tetra Cyclizations 9.4.1 Addition to a Double Bond and Then an Aromatic Ring 9.4.2 Addition to Two Double Bonds 9.4.3 Triple and Tetra Cyclizations 9.4.3.1 Triple Cyclizations 9.4.3.2 Tetracyclizations 9.5 Asymmetric Induction 9.6 Oxidations of Ketones 9.7 Summary and Conclusions 9.8 Addendum References Chapter 10 Manganese‐Catalyzed Dihydroxylation and Epoxidation of Olefins 10.1 Introduction 10.2 Oxidant 10.3 Use of Additives 10.4 In Situ Generated Catalysts 10.5 Activation of H2O2: Beyond High Valent Manganese Intermediates 10.6 Enantioselective Manganese‐Based Oxidation Catalysts 10.7 Conclusions References Index EULA