Iridium Complexes in Organic Synthesis (eBook)

Luis A. Oro is the head of the Homogeneous Catalysis Institute and professor of Inorganic Chemistry in the University of Zaragoza. His main research interests are in organometallic chemistry of platinum group metals where he has coauthored about 500 scientific contributions, and edited several books. He is member of the Interantional Advisory Board of Angewandte Chemie, and other international journals. He has received several scientific awards, including the Humboldt award, King Jaime prize, Solvay prize and Sacconi Medal. He is Doctor Honoris Causae by Rennes University. He is also member of the Deutsche Akademie der Naturforscher Leopoldina, the Academia Europaea, and foreign member of the Académie des Sciences. Carmen Claver is Professor of Inorganic Chemistry at the University Rovira I Virgili in Tarragona (Spain). She has co-authored about 200 scientific contributions in the field of enantioselective synthesis. She has also participated in the edition and publication of several books. She has received several scientific awards, being recognised in 2003 as distinguished research for the Catalan Government.

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 C 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 C