Axially Chiral Compounds AsymmetricSynthesis and Applications.

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Cover Title Page Contents Preface Part I Asymmetric Synthesis 1 Introduction and Characteristics 1.1 Introduction and Classification 1.2 Specification of Configuration References 2 Metal-Catalyzed Asymmetric Synthesis of Biaryl Atropisomers 2.1 Introduction 2.2 Biaryl Coupling 2.2.1 Cross-coupling 2.2.2 Other Types of Cross-coupling 2.2.3 Oxidative Coupling 2.3 Desymmetrization and (Dynamic) Kinetic Resolution via Functional Group Transformation 2.3.1 Desymmetrization of Prochiral Biaryls 2.3.2 Kinetic Resolution of Racemic Axially Chiral Biaryls 2.3.3 Dynamic Kinetic Resolution of Racemic Axially Chiral Biaryls 2.3.4 Ring-opening Reactions 2.4 Formation of Aromatic Ring via [2 + 2 + 2] Cycloaddition 2.4.1 Cobalt-Catalyzed Enantioselective [2 + 2 + 2] Cycloadditions 2.4.2 Rhodium-Catalyzed Enantioselective [2 + 2 + 2] Cycloadditions 2.4.3 Iridium-Catalyzed Enantioselective [2 + 2 + 2] Cycloadditions 2.5 CH Bond Functionalization 2.5.1 Chiral Catalyst-Controlled CH Bond Functionalization 2.5.2 Chiral Auxiliary-Induced CH Bond Functionalization 2.5.3 Atroposelective CH Arylation 2.6 Summary and Conclusions References 3 Organocatalytic Asymmetric Synthesis of Biaryl Atropisomers 3.1 Introduction 3.2 Atroposelective Synthesis of Biaryls by Kinetic Resolution Strategy 3.2.1 Conventional Kinetic Resolution 3.2.2 Dynamic Kinetic Resolution Strategy 3.3 Atroposelective Synthesis of Biaryls by Desymmetrization Strategy 3.4 Atroposelective Arene Formation to Access Axially Chiral Biaryls 3.4.1 Intramolecular Atroposelective Arene Formation 3.4.2 Atroposelective Arene Formation via Intermolecular Annulation 3.5 Atroposelective Synthesis of Biaryls via Direct C–H Arylation Strategy 3.5.1 Organocatalytic C–H Arylation by [3,3]-Sigmatropic Rearrangement 3.5.2 Atroposelective Arylation Based on Quinone Derivatives 3.5.3 Atroposelective Nucleophilic Aromatic Substitution 3.6 Conclusion References 4 Enantioselective Synthesis of Heterobiaryl Atropisomers 4.1 Introduction 4.2 Atropisomeric Heterobiaryls Featuring Two Six-Membered Rings 4.2.1 Functionalization of Heterobiaryls 4.2.2 Atroposelective Ring Formation 4.3 Atropisomeric Heterobiaryls Featuring a Five-Membered Ring 4.3.1 From Preformed Cyclic Systems 4.3.2 Formation of the Heterobiaryl Axis 4.3.3 Atroposelective Ring Formations 4.4 Atropisomeric Heterobiaryls Featuring Two Five-Membered Rings 4.4.1 Functionalization of Heterobiaryls 4.4.2 Aromatization of a Bis-heterocycle 4.4.3 Atroposelective Ring Formations 4.5 Conclusion and Outlook References 5 Asymmetric Synthesis of Nonbiaryl Atropisomers 5.1 Introduction 5.2 Styrenes 5.2.1 Axially Chiral Styrenes via Point-to-Axial Chirality Transfer 5.2.2 Axially Chiral Styrenes Controlled by Chiral Auxiliary 5.2.3 Metal-Catalyzed Enantioselective Synthesis of Axially Chiral Styrene 5.2.4 Organocatalytic Synthesis of Axially Chiral Styrenes 5.3 Amides 5.3.1 Stereochemical Stability of Atropisomeric Amides 5.3.2 Lithiation of Atropisomeric Amides to Access Various Alkylations 5.3.3 Syntheses of Atropisomerically Stable Amides via Chiral Auxiliaries 5.3.4 Catalytic Asymmetric Dihydroxylation via Sharpless KR Conditions 5.3.5 Atroposelective Aldol Reactions via DKR Approach 5.3.6 Atroposelective Halogenation of Aromatic Amides 5.3.7 Atroposelective [2 + 2 + 2] Cycloaddition Toward Atropisomerically Stable Benzamides 5.3.8 Enantioselective O-alkylation of Axially Chiral Amides 5.4 Diaryl Ethers 5.4.1 Resolution Studies of Diaryl Ethers 5.4.2 Enantioselective Synthesis of Diaryl Ether 5.4.3 Enzyme-Catalyzed Synthesis of Diaryl Ether 5.4.4 Synthesis of Scaffolds Related to Diaryl Ethers via Csp2-H Activation 5.5 Anilides 5.5.1 Stereochemical Stability of Axially Chiral Anilides 5.5.2 Kinetic Resolution or DKR to Access Axially Chiral Anilides 5.5.3 Synthesis of Axially Chiral Anilides via Planar to Axial Chirality Transfer 5.5.4 Metal-Catalyzed Synthesis of Chiral Anilides 5.5.5 Organocatalytic Synthesis of Chiral Anilides 5.6 Lactams and Related Scaffolds 5.6.1 Stereochemical Stability of Atropisomeric Lactams 5.6.2 Diastereoselective Cyclization Toward Atropisomeric Lactams 5.6.3 Enantioselective N-arylation Toward Lactam Atropisomers 5.6.4 Atroposelective [2 + 2 + 2] Cycloaddition with Isocyanates 5.6.5 Chiral Auxiliary Approach Toward Resolving Atropisomeric Lactams 5.6.6 Enantioselective Brønsted Base-Catalyzed Tandem Isomerization–Michael Reactions Toward Atropisomeric Lactams 5.7 Diaryl Amines 5.7.1 Stereochemical Stability of Diaryl Amines 5.7.2 Atroposelective Approaches Toward Diaryl Amines or Related Scaffolds References 6 Asymmetric Synthesis of Chiral Allenes 6.1 Introduction 6.2 Substrate- and Reagent-Controlled Chiral Allenes Synthesis: Stoichiometric Asymmetric Reactions 6.2.1 Chirality Transfer 6.2.2 Asymmetric Reaction with Stoichiometric Chiral Reagents 6.3 Catalytic Asymmetric Strategies for the Syntheses of Chiral Allenes 6.3.1 Catalytic Enantioselective Synthesis from Achiral Substances 6.3.2 Enantioselective Allene Synthesis from Chiral Substrates 6.4 Conclusion and Perspective References 7 Asymmetric Synthesis of Axially Chiral Natural Products 7.1 Introduction 7.2 Diastereoselective Coupling—Point to Axial Chirality Transfer 7.2.1 Intramolecular Diastereoselective Coupling 7.2.2 Intermolecular Diastereoselective Aryl Coupling 7.3 Atroposelective Aryl Coupling with Chiral Catalyst 7.3.1 Catalytic Oxidative Aryl Coupling 7.3.2 Transition Metal-Catalyzed Atroposelective Aryl Coupling 7.4 Asymmetric Transformation of Biaryls 7.4.1 Dynamic Kinetic Resolution of Biaryl Structure – The Lactone Method 7.4.2 Desymmetrization of Prostereogenic Biaryls 7.4.3 Catalytic Atroposelective C–H Functionalization of Biaryls 7.4.4 Diastereoselective Synthesis from Racemic Biaryls 7.5 Atroposelective Aromatization 7.6 Diastereoselective Macrocyclization 7.7 Conclusions and Perspectives References Part II Applications 8 Asymmetric Transformations 8.1 Asymmetric Transformation of Axially Chiral Biaryls and Heterobiaryls 8.1.1 Asymmetric Transformations with Preservation of Axially Chiral Backbone 8.1.2 Asymmetric Transformations with Axial-to-central Chirality Transfer 8.2 Asymmetric Transformation of Axially Chiral Non-biaryl Compounds 8.2.1 Cycloadditions and Cyclizations 8.2.2 Reaction with Nucleophiles 8.2.3 Reaction with Electrophiles 8.2.4 Photoreactions 8.3 Asymmetric Transformation of Chiral Allenes 8.3.1 Cyclization 8.3.2 Cycloaddition 8.3.3 Reaction with Nucleophiles 8.3.4 Chiral Allene as Nucleophiles 8.4 Conclusion References 9 Application for Axially Chiral Ligands 9.1 Introduction 9.2 Monodentate Phosphines 9.2.1 Asymmetric Hydrogenations 9.2.2 Asymmetric Hydrosilylation of Olefins 9.2.3 Asymmetric Allylic Substitutions 9.2.4 Miscellaneous Catalytic Asymmetric Transformations 9.3 Diphosphine Ligands 9.3.1 Hydrogenation Reactions 9.3.2 CC Bond Formation 9.3.3 CX Bond Formation 9.4 Phosphoramidite and Phosphamide Ligands 9.4.1 Asymmetric Conjugate Addition with Organometallic Nucleophiles 9.4.2 Hydrogenation 9.4.3 Hydroboration/Hydrosilylation Reactions 9.4.4 Allylic Substitutions 9.4.5 Other Asymmetric Transformations 9.5 N–P Ligands 9.5.1 Applications of N, P-Ligands 9.6 C2-Symmetric Diols 9.6.1 Mukaiyama Aldol Condensation Reactions 9.6.2 Diels–Alder Reaction 9.6.3 Arrangement Reaction 9.6.4 Reductive Reactions 9.7 Other Axially Chiral Ligands in Asymmetric Transformations 9.8 Conclusions References 10 Application for Axially Chiral Organocatalysts 10.1 Introduction 10.2 Chiral Brønsted Acid Catalysts 10.2.1 Chiral BINOL Derivatives 10.2.2 Chiral Phosphoric Acid 10.3 Chiral Counteranion Catalysts and Chiral Phase Transfer Catalysts 10.4 Brønsted Base Catalyst 10.5 Lewis Base Catalysts References 11 Application in Drugs and Materials 11.1 Drugs 11.2 Chiral Recognition 11.3 Chiral Additives in Liquid Crystals References Index EULA