Chiral Ferrocenes in Asymmetric Catalysis

Abstract

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 PR 2 Groups Attached to the Cp Ring. 4.3 Type B One PR 2 Group Attached to the Cp Ring, one PR 2 Group Attached to the alpha-Position of the Side Chain. 4.4 Type C One PR 2 Group Attached to the Cp Ring, one PR 2 Group Attached to the beta-Position of the Side Chain. 4.5 Type D, One PR 2 Group Attached to the Cp Ring, One PR 2 Group Attached to Other Positions of the Side Chain. 4.6 Type E, Both PR 2 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 Garcia Mancheno, 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 Rodriguez 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.