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| Preface | |
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| Introduction | |
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| Scope | |
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| History | |
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| Polarimetry and Optical Rotation | |
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| References | |
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| Structure | |
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| Meaning, Factorization, Internal Coordinates, Isomers | |
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| Constitution | |
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| Configuration | |
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| Conformation | |
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| Determination of Structure | |
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| A Priori Calculation of Structure | |
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| Molecular Models | |
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| References | |
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| Stereoisomers | |
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| Nature of Stereoisomers | |
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| General | |
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| Barriers Between Stereoisomers and Residual Stereoisomers | |
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| Enantiomers | |
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| Diastereomers | |
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| General Cases | |
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| Degenerate Cases | |
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| References | |
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| Symmetry | |
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| Introduction | |
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| Symmetry Elements | |
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| Symmetry Operators and Symmetry Point Groups | |
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| Point Groups Containing Chiral Molecules | |
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| Point Groups Containing Only Achiral Molecules | |
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| Averaged Symmetry | |
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| Symmetry and Molecular Properties | |
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| Rotation of Polarized Light | |
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| Dipole Moment | |
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| Symmetry Number | |
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| References | |
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| Configuration | |
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| Definitions: Relative and Absolute Configuration | |
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| Absolute Configuration and Notation | |
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| Determination of Absolute Configuration | |
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| Bijvoet Method | |
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| Theoretical Approaches | |
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| Modification of Crystal Morphology in the Presence of Additives | |
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| Relative Configuration and Notation | |
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| Determination of Relative Configuration of Saturated Aliphatic Compounds | |
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| X-Ray Structure Analysis | |
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| Chemical Interconversion Not Affecting Bonds to the Stereogenic Atom | |
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| Methods Based on Symmetry Considerations | |
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| Correlation Via Compounds with Chiral Centers of Two Types | |
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| The Method of Quasi-Racemates | |
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| Chemical Correlations Affecting Bonds to a Chiral Atom in a "Known" Way (For an overview, see ref. 32.) | |
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| Correlation by Stereoselective Synthesis of "Known" Stereochemical Course | |
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| Chiroptical, Spectroscopic, and Other Physical Methods | |
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| Conclusion: Network Arguments | |
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| References | |
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| Properties of Stereoisomers and Stereoisomer Discrimination | |
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| Introduction | |
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| Stereoisomer Discrimination | |
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| The Nature of Racemates | |
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| Properties of Racemates and of Their Enantiomer Components | |
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| Introduction | |
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| Optical Activity | |
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| Crystal Shape | |
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| Density and Racemate Type | |
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| Melting Point | |
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| Solubility | |
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| Vapor Pressure | |
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| Infrared Spectra | |
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| Electronic Spectra | |
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| Nuclear Magnetic Resonance Spectra | |
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| X-Ray Spectra | |
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| Liquid State and Interfacial Properties | |
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| Chromatography | |
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| Mass Spectrometry | |
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| Interaction with Other Chiral Substances | |
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| Biological Properties | |
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| Origins of Enantiomeric Homogeneity in Nature | |
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| Determination of Enantiomer and Diastereomer Composition | |
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| Introduction | |
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| Chiroptical Methods | |
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| NMR Methods Based on Diastereotopicity | |
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| Chromatographic and Related Separation Methods Based on Diastereomeric Interactions | |
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| Kinetic Methods | |
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| Miscellaneous Methods | |
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| References | |
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| Separation of Stereoisomers, Resolution, and Racemization | |
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| Introduction | |
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| Separation of Enantiomers by Crystallization | |
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| Crystal Picking and Triage | |
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| Conglomerates | |
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| Preferential Crystallization | |
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| Asymmetric Transformation of Racemates and Total Spontaneous Resolution | |
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| Chemical Separation of Enantiomers via Diastereomers | |
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| Formation and Separation of Diastereomers; Resolving Agents | |
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| Resolution Principles and Practice | |
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| Separation Via Complexes and Inclusion Compounds | |
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| Chromatographic Resolution | |
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| Asymmetric Transformations of Diastereomers | |
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| General Methods for the Separation of Diastereomers | |
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| Enantiomeric Enrichment and Resolution Strategy | |
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| Kinetic Resolution | |
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| Theory and Stoichiometric and Abiotic Catalytic Kinetic Resolution | |
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| Enzymatic Resolution | |
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| Miscellaneous Separation Methods | |
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| Racemization | |
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| Racemization Processes | |
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| Racemization of Amino Acids | |
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| References | |
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| Heterotopic Ligands and Faces: Prostereoisomerism and Prochirality | |
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| Introduction and Terminology | |
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| Significance and History | |
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| Homotopic and Heterotopic Ligands and Faces | |
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| Homotopic Ligands and Faces | |
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| Enantiotopic Ligands and Faces | |
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| Diastereotopic Ligands and Faces | |
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| Concepts and Nomenclature | |
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| Heterotopicity and Nuclear Magnetic Resonance | |
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| General Principles. Anisochrony | |
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| NMR in Assignment of Configuration and of Descriptors of Prostereoisomerism | |
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| Origin of Anisochrony | |
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| Conformationally Mobile Systems | |
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| Heterotopic Ligands and Faces in Enzyme-Catalyzed Reactions | |
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| Heterotopicity and Stereoelective Synthesis | |
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| Heterotopicity and Enzyme-Catalyzed Reactions | |
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| References | |
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| Stereochemistry of Alkenes | |
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| Structure of Alkenes and Nature of cis-trans Isomerism | |
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| General | |
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| Nomenclature | |
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| Cumulenes | |
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| Alkenes with Low Rotational Barriers and Nonplanar Alkenes | |
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| The C=N and N=N Double Bonds | |
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| Determination of Configuration of cis-trans Isomers | |
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| Chemical Methods | |
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| Physical Methods | |
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| Interconversion of cis-trans Isomers: Position of Equilibrium and Methods of Isomerization | |
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| Position of cis-trans Equilibria | |
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| Methods of Equilibration | |
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| Directed cis-trans Interconversion | |
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| References | |
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| Conformation of Acyclic Molecules | |
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| Conformation of Ethane, Butane, and Other Simple Saturated Acyclic Molecules | |
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| Alkanes | |
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| Saturated Acyclic Molecules with Polar Substituents or Chains and the Anomeric Effect | |
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| Conformation of Unsaturated Acyclic and Miscellaneous Compounds | |
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| Unsaturated Acyclic Compounds | |
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| Alkylbenzenes | |
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| Miscellaneous Compounds | |
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| Physical and Spectral Properties of Diastereomers and Conformers | |
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| General | |
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| Dipole Moments | |
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| Infrared Spectra | |
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| NMR Spectroscopy | |
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| Conformation and Reactivity: The Winstein-Holness Equation and the Curtin-Hammett Principle | |
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| References | |
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| Configuration and Conformation of Cyclic Molecules | |
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| Stereoisomerism and Configurational Nomenclature of Ring Compounds | |
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| Determination of Configuration of Substituted Ring Compounds | |
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| Introduction | |
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| Symmetry-Based Methods | |
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| Methods Based on Physical and Chemical Properties | |
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| Correlation Methods | |
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| Stability of Cyclic Molecules | |
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| Strain | |
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| Ease of Cyclization as a Function of Ring Size | |
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| Ease of Ring Closure as a Function of the Ring Atoms and Substitutents: The Thorpe-Ingold Effect | |
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| Baldwin's Rules | |
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| Conformational Aspects of the Chemistry of Six-Membered Ring Compounds | |
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| Cyclohexane | |
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| Monosubstituted Cyclohexanes | |
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| Disubstituted and Polysubstituted Cyclohexanes | |
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| Conformation and Physical Properties in Cyclohexane Derivatives | |
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| Conformation and Reactivity in Cyclohexanes | |
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| sp[superscript 2] Hybridized Cyclohexyl Systems | |
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| Six-Membered Saturated Heterocycles | |
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| Chemistry of Ring Compounds Other than Six-Membered Ones | |
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| Three-Membered Rings | |
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| Four-Membered Rings | |
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| Five-Membered Rings | |
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| Rings Larger Than Six-Membered | |
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| Stereochemistry of Fused, Bridged, and Caged Ring Systems | |
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| Fused Rings | |
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| Bridged Rings | |
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| Propellanes | |
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| Catenanes, Rotaxanes, Knots, and Mobius Strips | |
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| Cubane, Tetrahedrane, Dodecahedrane, Adamantane, and Buckminsterfullerene | |
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| References | |
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| Chiroptical Properties | |
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| Introduction | |
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| Optical Activity and Anisotropic Refraction | |
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| Origin and Theory | |
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| Optical Rotatory Dispersion | |
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| Circular Dichroism and Anisotropic Absorption | |
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| Applications of Optical Rotary Dispersion and Circular Dichroism | |
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| Determination of Configuration and Conformation: Theory | |
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| Classification of Chromophores | |
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| Sector and Helicity Rules | |
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| Exciton Chirality | |
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| Other Applications: Induced ORD and CD | |
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| Circular Dichroism of Chiral Polymers | |
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| Applications of Optical Activity | |
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| Polarimetry | |
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| Empirical Rules and Correlations: Calculation of Optical Rotation | |
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| Vibrational Optical Activity | |
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| References | |
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| Chirality in Molecules Devoid of Chiral Centers | |
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| Introduction and Nomenclature | |
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| Allenes | |
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| Historical Overview and Natural Occurrence | |
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| Synthesis of Optically Active Allenes | |
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| Determination of Configuration and Enantiomeric Purity of Allenes | |
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| Cyclic Allenes, Cumulenes, and Ketene Imines | |
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| Alkylidenecycloalkanes | |
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| Spiranes | |
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| Biphenyls and Atropisomerism | |
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| Introduction | |
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| Biphenyls and Other Atropisomers of the sp[superscript 2]-sp[superscript 2] Single-Bond Type | |
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| Atropisomerism About sp[superscript 2]-sp[superscript 3] Single Bonds | |
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| Atropisomerism About sp[superscript 3]-sp[superscript 3] Bonds | |
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| Molecular Propellers | |
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| Helicenes | |
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| Molecules with Planar Chirality | |
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| Introduction | |
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| Cyclophanes | |
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| trans-Cycloalkenes | |
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| Metallocenes and Related Compounds | |
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| References | |
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| Index | |