Chiral Ferrocenes In Asymmetric Catalysis Synthesis And Applications

This book meets the long-felt need for a reference on ferrocenes with the focus on catalysis. It provides a thorough overview of the synthesis and characterization of different types of chiral ferrocene ligands, their application to various catalytic asymmetric reactions, and versatile chiral materials as well as drug intermediates synthesized from them. Written by the "who's who" of ferrocene catalysis, this is a guide to the design of new ferrocene ligands and synthesis of chiral synthetic intermediates, and will thus be useful for organic, catalytic and synthetic chemists working in academia, industrial research or process development.

Li-Xin Dai is Professor at the Shanghai Institute of Organic Chemistry (SIOC), Chinese Academy of Sciences. He graduated from Zhejiang University in 1947 and joined the SIOC in 1953. He is the Honorary President of Shanghai Society of Chemistry and Chemical Industry, and the Chairman of the Academic Committee of the State Key Laboratory of Elemento-Organic Chemistry in Nankai University. His research interests include the design of chiral ligands and their applications in asymmetric catalysis. He was elected as the Member of the Chinese Academy of Sciences in 1993. He has authored over 150 scientific publications and has received numerous scientific awards, including Ho Leung Ho Lee Prize and the National Natural Science Award of China.

Xue-Long Hou received his PhD in 1986 from the Shanghai Institute of Organic Chemistry (SIOC), Chinese Academy of Sciences under the mentorship of Professors Wei Yuan Huang of SIOC and Henry N.C. Wong of the Chinese University of Hong Kong. He was awarded an Alexander von Humboldt research fellowship and completed two years of postdoctoral research with Professor Emanuel Vogel at Cologne University, Germany. He is currently Professor at the SIOC and his research interests include OMCOS, the design of chiral ligands and their applications in asymmetric catalysis and the transformation of organic molecules under non-metal conditions.

List of Contributors.

1. Introduction (Li-Xin Dai and Xue-Long Hou).

1.1 Foreword.

1.2 Planar Chirality of Ferrocenyl Ligands.

1.3 Derivatization of the Ferrocene Scaffold.

1.4 Stability, Rigidity and Bulkiness of the Ferrocene Scaffold.

1.5 Outlook.

References.

2. Stereoselective Synthesis of Planar Chiral Ferrocenes (Wei-Ping Deng, Victor Snieckus, and Costa Metallinos).

2.1 Introduction.

2.2 Diasteroselective Directed ortro-Metalation of Ferrocenes with Chiral Auxiliaries.

2.3 Enantioselective Drected ortro-Metalation of Ferrocenes with Chiral Bases.

2.4 Enzymatic and Nonenzymatic Kinetic Resolutions.

2.5 Summary and Perspectives.

2.6 Selected Experimental Procedures.

References.

3. Monodentate Chiral Ferrocenyl Ligands (Ji-Bao Xia, Timothy F. Jamison, and Shu-Li You).

3.1 Introduction.

3.2 Nickel-Catalyzed Asymmetric Reductive Coupling Reactions.

3.3 Copper(I)-Catalyzed Asymmetric Allylic Alkylation Reactions.

3.4 Asymmetric Suzuki-Miyaura Reactions.

3.5 Addition of Organoaluminum to Aldehydes and Enones.

3.6 Asymmetric Nucleophilic Catalysis.

3.7 Conclusion and Pespectives.

References.

4. Bidentate 1,2-Ferrocenyl Diphosphine Ligands (Hans-Ulrich Blaser and Matthias Lotz).

4.1 Introduction.

4.2 Type A Both PR₂ Groups Attached to the Cp Ring.

4.3 Type B One PR₂ Group Attached to the Cp Ring, one PR₂ Group Attached to the α-Position of the Side Chain.

4.4 Type C One PR₂ Group Attached to the Cp Ring, one PR₂ Group Attached to the β-Position of the Side Chain.

4.5 Type D, One PR₂ Group Attached to the Cp Ring, One PR₂ Group Attached to Other Positions of the Side Chain.

4.6 Type E, Both PR₂ Groups Attached to Side Chains.

References.

5. 1,2-P,N-Bidentate Ferrocenyl Ligands (Yong Gui Zhou and Xue Long Hou).

5.1 Introduction.

5.2 Asymmetric Hydrogenation and Asymmetric Transfer Hydrogenation.

5.3 Formation of a C-C Bond.

5.4 Cycloaddition Reactions.

5.5 Miscellaneous Reactions.

5.6 Conclusion and Perspectives.

5.7 Experimental: Selected Procedures.

References.

6. N,O-Bidentate Ferrocenyl Ligands (Anne Nijs, Olga García Mancheño, and Carsten Bolm).

6.1 Introduction.

6.2 Addition of Organozinc Reagents to Aldehydes.

6.3 Addition to Aldehydes with Boron Reagents.

6.4 Other Transformations: Asymmetric Epoxidation.

6.5 Conclusion and Perspectives.

References.

7. Symmetrical 1,1’-Bidentate Ferrocenyl Ligands (Wanbin Zhang and Delong Liu).

7.1 Introduction.

7.2 Symmetrical 1,1’-Disubstituted Ferrocenyl Ligands.

7.3 Symmetrical 1,1’,2,2’-Tetrasubstituted Ferrocenyl Ligands.

7.4 Analogs of Ferrocenes: Symmetrical 1,1’-Bidentate Ruthenocenyl Ligands.

7.5 Conclusion and Perspectives.

7.6 Experimental: Selected Procedures.

References.

8. Unsymmetrical 1,1’-Bidentate Ferrocenyl Ligands (Shu-Li You).

8.1 Introduction.

8.2 Palladium-Catalyzed Asymmetric Allylic Substitution Reaction.

8.3 Gold or Silver-Catalyzed Asymmetric Aldol Reactions.

8.4 Asymmetric Hydrogenation.

8.5 Asymmetric Cross-Coupling Reaction.

8.6 Asymmetric Heck Reaction.

8.7 Miscellaneous.

8.8 Conclusion and Perspectives.

8.9 Experimental: Selected Procedures.

References.

9. Sulfur- and Selenium-Containing Ferrocenyl Ligands (Juan C. Carretero, Javier Adrio, and Marta Rodríguez Rivero).

9.1 Introduction.

9.2 Asymmetric Allylic Substitution.

9.3 Other Asymmetric Palladium-Catalyzed Reactions.

9.4 Gold-Catalyzed Reactions.

9.5 Asymmetric Reductions.

9.6 Asymmetric 1,2- and 1,4-Nucleophilic Addition.

9.7 Asymmetric Cycloaddition Reactions.

9.8 Asymmetric Nucleophilic Catalysis.

9.9 Conclusion and Perspectives.

9.10 Experimental: Selected Procedures.

References.

10. Biferrocene Ligands (Ryoichi Kuwano).

10.1 Introdution.

10.2 Trans-Chelating Chiral Bisphosphines: TRAP.

10.3 2,2-Bis(diarylphosphino)-1,1-biferrocenes: BIFEP.

10.4 Miscellaneous Biferrocene-Based Chiral Ligands.

10.5 Conclusion.

References.

11. Applications of Aza- and Phosphaferrocenes and Related Compounds in Asymmetric Catalysis (Nicolas Marion and Gregory C. Fu).

11.1 Introduction.

11.2 Background on Aza- and Phosphaferrocenes.

11.3 Azaferrocenes in Catalysis.

11.4 Phosphaferrocenes in Catalysis.

11.5 Conclusions.

References.

12. Metallocyclic Ferrocenyl Ligands (Christopher J. Richards).

12.1 Introduction.

12.2 Asymmetric Synthesis of Planar Chiral Metallocyclic Complexes.

12.3 Stoichiometric Synthetic Applications of Scalemic Planar Chiral Metallocyclic Complexes.

12.4 Asymmetric Catalysis with Scalemic Planar Chiral Palladocyclic Complexes.

12.5 Conclusion.

References.

A.Show Case of the Most Effective Chiral Ferrocene Ligands in Various Catalytic Reactions.

A.1 Asymmetric Allylic Substitution Reactions.

A.2 Asymmetric Aldol Reactions.

A.3 Asymmetric Cycloaddition Reactions.

A.4 Asymmetric Hydrogenation.

A.5 Pd-Catalyzed Asymmetric Heck Reaction.

A.6 Addition of Organozinc Reagents.

A.7 Asymmetric Rearrangement of Allylic Imidates.

A.8 Cu-Catalyzed Cyclopropanation.

A.9 Coupling Reaction of Vinyl Bromide and 1-Phenylethylzinc Chloride.

A.10 Enantioselective Intromolecular Aminopalladation.

A.11 Nickel-Catalyzed Asymmetric Three-Component Coupling of Alkynes, Imines, and Organoboron Reagents.

A.12 Reactions with Ketenes.

A.13 Ring Opening Reaction.

Index.