P-Stereogenic Ligands in Enantioselective Catalysis -- Contents -- Chapter 1 Introduction -- 1.1 Historical Overview -- 1.2 Configurational Stability of P-Stereogenic Compounds -- 1.3 Interconversions between P-Stereogenic Compounds -- 1.3.1 Phosphines, Phosphine Oxides and Sulfides -- 1.3.2 Phosphines and Phosphine Boranes -- References -- Chapter 2 Resolution of Racemic and Diastereomeric Mixtures -- 2.1 Introduction -- 2.2 Resolution of Racemic Mixtures -- 2.2.1 Direct Resolutions with Non-metallic Auxiliaries -- 2.2.2 Direct Resolutions with Cyclometallated Pd Complexes -- 2.2.3 Direct Resolutions by ChromatographicMethods -- 2.2.4 Dynamic Resolution of Secondary Phosphine Boranes -- 2.3 Resolution of Diastereomeric Mixtures -- 2.3.1 Menthol as a Chiral Auxiliary -- 2.3.1.1 Menthylphosphinates and Related Compounds -- 2.3.1.2 Menthylphosphinite Boranes and Related Compounds -- 2.3.1.3 Other Syntheses Based on Menthol -- 2.3.2 Other Chiral Auxiliaries -- 2.4 Chiral Ligands Made by Enantioselective Synthesis -- 2.4.1 Chiral Alcohols and Amines -- 2.4.2 Chiral Ferrocenes -- 2.4.3 Chiral Biaryls -- 2.4.4 Other Chiral Backbones -- 2.5 Cyclometallated Pd Complexes as Templates -- References -- Chapter 3 P-Stereogenic Heterocycles -- 3.1 Introduction -- 3.2 Diazaphospholidines and Derivatives -- 3.2.1 P(III) Tertiary Diazaphospholidines -- 3.2.2 P(V) Tertiary Diazaphospholidines -- 3.2.3 P(V) Secondary Diazaphospholidines -- 3.3 Oxazaphospholidines and Derivatives -- 3.3.1 Derived from Ephedrine -- 3.3.1.1 P(III) Oxazaphospholidines -- 3.3.1.2 P(V) Oxazaphospholidines -- 3.3.2 Derived from Prolinol -- 3.3.3 Derived from Other Amino Alcohols -- 3.3.3.1 Acyclic Amino Alcohols -- 3.3.3.2 Cyclic Amino Alcohols -- 3.4 Other Heterocycles -- 3.4.1 Five-membered Heterocycles -- 3.4.2 Six-membered Heterocycles -- 3.4.3 Seven-membered Heterocycles.

References -- Chapter 4 P-Stereogenic Compounds Derived from Enantiopure Heterocycles -- 4.1 Introduction -- 4.2 Overview of Different Methodologies -- 4.3 The Jugé-Stephan Method -- 4.3.1 Introduction of R2 by Nucleophilic Ring Opening -- 4.3.1.1 Ring Opening with Mono(organolithiums) -- 4.3.1.2 Ring Opening with Bis(organolithiums) -- 4.3.2 P-N Bond Cleavage by Acidolysis -- 4.3.2.1 Formation of Phosphinite Boranes -- 4.3.2.2 Formation of Chlorophosphine Boranes -- 4.3.3 Introduction of R3 by Nucleophilic Substitution -- 4.3.3.1 Nucleophilic Substitution on Phosphinite Boranes -- 4.3.3.2 Nucleophilic Substitution on Chlorophosphine Boranes -- 4.4 Extensions of the Jugé-Stephan Method -- 4.4.1 P-Stereogenic AMPP Ligands -- 4.4.2 Deprotonation of Methylphosphine Boranes -- 4.4.2.1 Monophosphines and Bidentate C1 Ligands -- 4.4.2.2 C2-Diphosphines -- 4.4.2.3 P-Stereogenic Dendrimers -- 4.4.3 Other Extensions -- 4.5 Other Methodologies -- 4.5.1 Variations of the Jugé-Stephan Method -- 4.5.1.1 Pentavalent Oxazaphospholidines Derived from Ephedrine -- 4.5.1.2 Trivalent Oxazaphospholidines Derived from Ephedrine -- 4.5.2 Other Chiral Auxiliaries -- 4.5.2.1 Chiral Amino Alcohols -- 4.5.2.2 Other Heterobifunctional Chiral Auxiliaries -- 4.6 Conclusion -- References -- Chapter 5 P-Stereogenic Phosphines Prepared by Enantioselective Deprotonation -- 5.1 Introduction -- 5.2 Deprotonation of Dimethylphosphine Derivatives -- 5.2.1 Dimethylphosphine Boranes -- 5.2.1.1 Monophosphines -- 5.2.1.2 C2-Diphosphines -- 5.2.1.3 BisP* Diphosphines -- 5.2.1.4 MiniPHOS Diphosphines -- 5.2.1.5 P-Stereogenic Dendrimers, Polyphosphines, Polymers and Macrocycles -- 5.2.2 Dimethylphosphine Sulfides -- 5.3 Deprotonation of Cyclic Phosphine Derivatives -- 5.3.1 Phosphetane Boranes and Sulfides -- 5.3.2 Phospholane Boranes, Sulfides and Oxides -- 5.5.3 Phosphorinane Boranes.

5.4 Extensions of the Method -- 5.4.1 Surrogates of (+)-Sparteine -- 5.4.2 Catalytic Enantioselective Deprotonation -- 5.4.3 Deprotonation of Other Substrates -- 5.5 Conclusions -- References -- Chapter 6 Preparation by Enantioselective Catalysis -- 6.1 Introduction -- 6.2 Metal-Catalysed Synthesis of P-Stereogenic Compounds -- 6.2.1 Metal Phosphido Complexes -- 6.2.2 Hydrophosphination of Alkenes and Alkynes -- 6.2.2.1 Pt-Catalysed Hydrophosphination -- 6.2.2.2 Ln-Catalysed Alkene Hydrophosphination -- 6.2.2.3 Pd-Catalysed Alkyne Hydrophosphination -- 6.2.3 Phosphination of Aryl Halides -- 6.2.3.1 Pd-Catalysed Arylation of Secondary Phosphines -- 6.2.3.2 Pd-Catalysed Arylation of Silylphosphines -- 6.2.3.3 Pd-Catalysed Arylation of Secondary Phosphine Boranes -- 6.2.4 Alkylation of Secondary Phosphines -- 6.2.4.1 Pt-Catalysed Alkylation of Secondary Phosphines -- 6.2.4.2 Ru-Catalysed Alkylation of Secondary Phosphines -- 6.2.5 Rh-Catalysed Desymmetrisation of Dialkynylphosphine Oxides -- 6.2.6 Ru- and Mo-Catalysed Metathesis -- 6.3 Biocatalytic Synthesis of P-Stereogenic Compounds -- 6.3.1 Kinetic Resolutions -- 6.3.2 Desymmetrisations of Phosphine Oxides and Phosphine Boranes -- 6.4 Conclusions -- References -- Chapter 7 Hydrogenation and Related Reactions -- 7.1 Introduction -- 7.2 Rh-Catalysed Hydrogenation -- 7.2.1 Hydrogenation of Alkenes -- 7.2.2 Mechanism -- 7.2.3 Hydrogenation of Ketones and Imines -- 7.3 Ru-, Ir- and Pd-Catalysed Hydrogenation -- 7.3.1 Ru-Catalysed Hydrogenation -- 7.3.2 Ir-Catalysed Hydrogenation -- 7.3.3 Pd-Catalysed Hydrogenation -- 7.4 Hydrosilylation -- 7.5 Hydrogen Transfer -- 7.6 Conclusion -- References -- Chapter 8 Miscellaneous Reactions -- 8.1 Introduction -- 8.2 Hydrovinylation -- 8.3 Hydroformylation -- 8.4 Allylic Substitution -- 8.4.1 Carbon Nucleophiles -- 8.4.2 Other Nucleophiles.

8.5 Reductive Coupling of Alkynes and Aldehydes -- 8.6 Conjugate Additions -- 8.6.1 Cu-Catalysed Additions -- 8.6.2 Rh-Catalysed Additions -- 8.7 Alkylative Ring Opening -- 8.8 Heck Reaction -- 8.9 Cycloaddition Reactions -- 8.10 Cyclopropanation -- 8.11 Hydroacylation -- 8.12 Arylcyanation -- 8.13 Arylation of Enolates -- 8.14 Hydroboration -- References -- Subject Index.