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Iridium Complexes in Organic Synthesis

Luis A. Oro (Editor), Carmen Claver (Editor)
ISBN: 978-3-527-31996-1
424 pages
February 2009
Iridium Complexes in Organic Synthesis (3527319964) cover image
Ranging from hydrogenation to hydroamination, cycloadditions and nanoparticles, this first handbook to comprehensively cover the topic of iridium in synthesis discusses the important advances in iridium-catalyzed reactions, namely the use of iridium complexes in enantioselective catalysis.
A must for organic, complex and catalytic chemists, as well as those working with/on organometallics.
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Preface.

List of Contributors.

1. Application of Iridium Catalysts in the Fine Chemicals Industry (Hans-Ulrich Bloser).

1.1 Introduction.

1.2 Industrial Requirements for Applying Catalysts.

1.3 Enantioselective Hydrogenation of C=N Bonds.

1.4 Enantioselective Hydrogenation of C=C Bonds.

1.5 Miscellaneous Catalytic Applications with Industrial Potential.

1.6 Conclusions and Outlook.

References.

2. Dihydrido Iridium Triisopropylphosphine Complexes: From Organometallic Chemistry to Catalysis (Luis A. Oro).

2.1 Introduction.

2.2 [Ir(COD) (NCMe) (PR₃)]BF₄ (PR₃ = P<sup>i</sup> Pr<sub>3</sub>, PMe<sub>3)</sub>] and Related Complexes as Catalyst Precursors: Is 1,5-Cyclo-octadiene an Innocent and Removable Ligand?

2.3 The Dihydrido Iridium Triisopropylphosphine Complex [IrH₂(NCMe)₃(P<sup>i</sup> Pr<sub>₃</sub>)]BF₄ as Alkyne Hydrogenation Catalysts.

2.4 The Dihydrido Iridium Triisopropylphosphine Complex [IrH₂(NCMe)₃(Pi r₃)]BF₄ as Alkene Hydrogenation Catalysts.

2.5 Dihydrido Arene Iridium Triisopropylphosphine Complexes.

2.6 Dihydrido Iridium Triisopropylphosphine Complexes as Imine Hydrogenation Catalysts.

2.7 Conclusions.

Acknowledgments.

References.

3. Iridium N-Heterocyclic Carbene Complexes and Their Application as Homogeneous Catalysts (Eduardo Peris and Robert H. Crabtree).

3.1 Introduction.

3.2 Types of Ir—NHC and Reactivity.

3.3 Catalysts with Ir—NHCs.

3.4 Conclusions.

References.

4. Iridium-Catalyzed C=O Hydrogenation (Claudio Bianchini, Luca Gonsalvi and Maurizio Peruzzini).

4.1 Introduction.

4.2 Homogenous C=O Hydrogenations.

4.3 Heterogeneous, Supported and Biocatalytic Hydrogenations.

References.

5. Catalytic Activity of Cp* Iridium Complexes in Hydrogen Transfer Reactions (Ken-ichi Fujita and Ryochei Yamaguchi).

5.1 Introduction.

5.2 Hydrogen Transfer Oxidation of Alcohols (Oppenauer-Type Oxidation).

5.3 Transfer Hydrogenation of Unsaturated Compounds.

5.4 Asymmetric Synthesis Based on Hydrogen Transfer.

5.5 Hydrogen Transfer Reactions in Aqueous Media.

5.6 Carbon-Nitrogen Bond Formation Based on Hydrogen Transfer.

5.7 Carbon-Carbon Bond Formation Based on Hydrogen Transfer.

5.8 Carbon-Oxygen Bond Formation Based on Hydrogen Transfer.

5.9 Dehydrogenative Oxidation of Alcohols.

5.10 Conclusions.

References.

6. Iridium-Catalyzed Hydroamination (Romano Dorta).

6.1 Introduction.

6.2 Iridium-Catalyzed Olefin Hydroamination (OHA).

6.3 Iridium-Catalyzed Alkyne Hydroamination (AHA).

6.4 Proposed Mechanisms.

6.5 Complexes and Reactions of Ir Relevant to Hydroamination.

6.6 Conclusions.

References.

7. Iridium-Catalyzed Boron-Addition (Elena Fernández and Anna M. Segarra).

7.1 Introduction.

7.2 Iridium-Boryl Complexes.

7.3 Hydroboration.

7.4 Diboration.

7.5 Borylation.

References.

8. Iridium-Catalyzed Methanol Carbonylation (Philippe Kalck and Philippe Serp).

8.1 Introduction.

8.2 Rhodium-Based Processes.

8.3 Iridium Reactivity in the Methanol Carbonylation Reaction.

8.4 The Iridium-Based Cativa Process.

8.5 The Iridium−Platinum Based Process.

8.6 The iridium−Cocatalyst Mechanism, and Conclusions.

Acknowledgments.

References.

9. Iridium-Catalyzed Asymmetric Allylic Substitutions (Günter Helmchen).

9.1 Introduction.

9.2 Ir-Catalyzed Allylic Substitutions: Fundamentals.

9.3 C-Nucleophiles.

9.4 N-Nucleophiles.

9.5 O-Nucleophiles.

9.6 Synthesis of Biologically Active Compounds via Allylic Substitution.

9.7 Conclusions.

Acknowledgments.

References.

10. Iridium-Catalyzed Coupling Reactions (Yasutaka Ishii, Yasushi Obora and Satoshi Sakaguchi).

10.1 Introduction.

10.2 Iridium-Catalyzed Dimerization and Cyclotrimerization of Alkynes.

10.3 Iridium-Catalyzed, Three-Component Coupling Reactions of Aldehydes, Amines and Alkynes.

10.4 Head-to-Tail Dimerization of Acrylates.

10.5 A Novel Synthesis of Vinyl Ethers via an Unusual Exchange Reaction.

10.6 Iridium-Catalyzed Allylic Substitution.

10.7 Alkylation of Ketones with Alcohols.

10.8 N-Alkylation of Amines.

10.9 Oxidative Dimerization of Primary Alcohols to Esters.

10.10 Iridium-Catalyzed Addition of Water and Alcohols to Terminal Alkynes.

10.11 Iridium-Catalyzed Direct Arylation of Aromatic C—H Bonds.

10.12 Iridium-Catalyzed Anti-Markovnikov Olefin Arylation.

10.13 Iridium-Catalyzed Silylation and Borylation of Aromatic C—H Bonds.

10.14 Miscellaneous Reactions Catalyzed by Iridium Complexes.

References.

11. Iridium-Catalyzed Cycloadditions (Takanori Shibata).

11.1 Introduction.

11.2 [2+2+2] Cycloaddition.

11.3 Enantioselective [2+2+2] Cycloaddition.
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11.4 [2+2+1] Cycloaddition.

11.5 [4+2] and [5+1] Cycloadditions.

11.6 Cycloisomerization.

11.7 Ir(III)-Catalyzed Cyclizations.

11.8 Miscellaneous Cycloadditions.

11.9 Conclusions.

References.

12. Pincer-Type Iridium Complexes for Organic Transformations (Martin Albrecht and David Morales-Morales).

12.1 Introduction.

12.2 Iridium PCP-Catalyzed Activation of C(sp³)—H Bonds in Unfunctionalized Alkanes.

12.3 Arene C(sp²)—H and Alkyne C(sp¹)—H Bond Activation.

12.4 C—E Bond Activation.

12.5 Ammonia Borane Dehydrogenation.

12.6 Conclusions.

Acknowledgments.

References.

13. Iridium-Mediated Alkane Dehydrogenation (David Morales-Morales).

13.1 Introduction.

13.2 Alkane C—H Activation with Ir Derivatives.

13.3 Alkane Dehydrogenation with Ir Complexes.

13.4 Alkane Dehydrogenation Catalyzed by Ir Pincer Complexes.

13.5 Final Remarks.

Acknowledgments.

References.

14. Transformations of (Organo) silicon Compounds Catalyzed by Iridium Complexes (Bogdan Marciniec and Ireneusz Kownacki).

14.1 Introduction.

14.2 Hydrosilylation and Dehydrogenative Silylation of Carbon−Carbon Multiple Bonds.

14.3 Asymmetric Hydrosilylation of Ketones and Imines.

14.4 Transformation of Organosilicon Compounds in the Presence of Carbon Monoxide.

14.5 Silylation of Aromatic Carbon−Hydrogen Bonds.

14.6 Silylation of Alkenes with Vinysilanes.

14.7 Alcoholysis and Oxygenation of Hydrosilanes.

14.8 Isomerization of Silyl Olefins.

14.9 Addition of silylacetglenes ≡C—H Bonds into Imines.

14.10 Conclusions.

References.

15. Catalytic Properties of Soluble Iridium Nanoparticles (Jackson D. Scholten and Jaïrton Dupont).

15.1 Introduction.

15.2 Synthesis of Soluble Iridium Nanoparticles.

15.3 Kinetic Studies of Iridium Nanoparticle Formation: The Autocatalytic Mechanism.

15.4 Catalytic Applications of Soluble Iridium Nanoparticles.

15.5 Conclusions.

References.

Index.

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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.
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This book provides good coverage of an increasingly important area and will be well worth reading by anyone interested in metal-catalyzed organic synthesis. (The Journal of the American Chemical Society, July 2009)

Both academic and industrial practitioners of transition-metal catalysis and organometallic chemistry will find this volume to be a very useful addition to their bookshelves. ( Angewandte Chemie International Edition , June 2009)

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