Iridium Complexes in Organic Synthesis

APPLICATION OF IRIDIUM CATALYSTS IN THE FINE CHEMICALS INDUSTRY Introduction Industrial Requirements for Applying Catalysts Enantioselective Hydrogenation of C=N Bonds Enantioselective Hydrogenation of C=C Bonds Miscellaneous Catalytic Applications with Industrial Potential DIHYDRIDO IRIDIUM TRIISOPROPYLPHOSPHINE COMPLEXES: FROM ORGANOMETALLIC CHEMISTRY TO CATALYSIS Introduction [Ir(COD)(NCMe)(PR3)]BF4 (PR=PiPr3, PMe3) and Related Complexes as Catalyst Precursors: Is 1,5-Cyclo-Octadiene an Innocent and Removable Ligand? The Dihydrido Iridium Triisopropylphosphine Complex [IrH2(NCMe)3(PiPr3)]BF4 as Alkene Hydrogenation Catalysts The Dihydrido Iridium Triisoprpylphosphine Complex [IrH2(NCMe)3(PiPr3)]BF4 as Alkyne Hydrogenation Catalysts Dihydrido Arene Iridium Triisopropylphosphine Complexes Dihydrido Iridium Triisopropylphosphine Complexes as Imine Hydrogenation Catalysts IRIDIUM N-HETEROCYCLIC CARBENE COMPLEXES AND THEIR APPLICATON AS HOMOGENEOUS CATALYSTS Introduction Types or Ir-NHC and Reactivity Catalysis with Ir-NHCs IRIDIUM-CATALYZED C=O HYDROGENATION Introduction Homogeneous C=O Hydrogenations Heterogeneous, Supported and Biocatalytic Hydrogenations CATALYTIC ACTIVITY OF Cp* IRIDIUM COMPLEXES IN HYDROGEN TRANSFER REACTONS Introduction Hydrogen Transfer Oxidation of Alcohols (Oppenauer-Type Oxidation) Transfer Hydrogenation of Unsaturated Compounds Asymmetric Synthesis Based on Hydrogen Transfer Hydrogen Transfer Reactions in Aqueous Media Carbon-Nitrogen Bond Formation Based on Hydrogen Transfer Carbon-Carbon Bond Formation Based on Hydrogen Transfer Carbon-Oxygen Bond Formation Based on Hydrogen Transfer Dehydrogenative Oxidation of Alcohols IRIDIUM-CATALYZED HYDROAMINATION Introduction Iridium-Catalyzed Olefin Hydroamination (OHA) Iridium-Catalyzed Alkyne Hydroamination (ASA) Proposed Mechanisms Complexes and Reactions of Ir Relevant to Hydroamination IRIDIUM-CATALYZED BORON-ADDITION Introduction Iridium-Boryl Complexes Hydroboration Diboration Borylation IRIDIUM-CATALYZED METHANOL CARBONYLATION Introduction Rhodium-Based Processes Iridium Reactivity in the Methanol Carbonylation Reaction The Iridium-Based Cativa Process The Iridium-Platinum-Based Process The Iridium-Cocatalyst Mechanism, and Conclusion Acknowledgments IRIDIUM-CATALYZED ASYMMETRIC ALLYLIC SUBSTITUTIONS Introduction Ir-Catalyzed Allylic Substitutions: Fundamentals C-Nucleophiles N-Nucleophiles O-Nucleophiles Synthesis of Biologically Active Compounds via Allylic Substitution IRIDIUM-CATALYZED COUPLING REACTIONS Introduction Iridium-Catalyzed Dimerization and Cyclotrimerization of Alkynes Iridium-Catalyzed, Three-Component Coupling Reactions of Aldehydes, Amines and Alkynes Head-to-Tail Dimerization of Acrylates A Novel Synthesis of Vinyl Ethers via an Unusual Exchange Reaction Iridium-Catalyzed Allylic Substitution Alkylation of Ketones with Alcohols N-Alkylation of Amines Oxidative Dimerization of Primary Alcohols to esters Iridium-Catalyzed Addition of Water and Alcohols to Terminal Alkynes Iridium-Catalyzed Direct Arylation of Aromatic C-H Bonds Iridium-Catalyzed Anti-Markovnikov Olefin Arylation Iridium-Catalyzed Silylation and Borylation of Aromatic C-H Bonds Miscellaneous Reactions Catalyzed by Iridium Complexes IRIDIUM-CATALYZED CYCLOADDITIONS Introduction [2+2+2] Cycloaddition Enantioselective [2+2+2] Cycloaddition [2+2+1] Cycloaddition [4+2] and [5+1] Cycloaddition Cycloisomerization Ir(III)-Catalyzed Cyclizations Miscellaneous Cycloadditions PINCER-TYPE IRIDIUM COMPLEXES FOR ORGANIC TRANSFORMATIONS Introduction Iridium PCP-Catalyzed Activation of C(sp3)-H Bonds in Unfunctionalized Alkanes Arene C(sp2)-H and Alyne C(sp1)-H Bond Activation C-E Bond Activation Ammonia Borane Dehydrogenation IRIDIUM-MEDIATED ALKANE DEHYDROGENATION Introduction Alkane C-H Activation with Ir Derivatives Alkane Dehydrogenation with Ir Complexes Alkane Dehydrogenation Catalyzed by Ir Pincer Complexes TRANSFORMATIONS OF (ORGANO)SILICON COMPOUNDS CATALYZED BY IRIDIUM COMPLEXES Introduction Hydrosilylation and Dehydrogenative Silylation of Carbon-Carbon Multiple Bonds Asymmetric Hydrosilylation of Ketones and Imines Transformation of Organosilicon Compounds in the Presence of Carbon Monoxide Silylation of Aromatic Carbon-Hydrogen Bonds Silylation of Alkenes with Vinylsilanes Alcoholysis and Oxygenation of Hydrosilanes Isomerization of Silyl Olefins Addition of Silylacetglenes C-H Bonds into Imines CATALYTIC PROPERTIES OF SOLUBLE IR IDIUM NANOPARTICLES Introduction Synthesis of Soluble Iridium Nanoparticles Kinetic Studies of Iridium Nanoparticle Formation: The Autocatalytic Mechanism Catalytic Applications of Soluble Iridium Nanoparticles