Stereochemistry of organic compounds : principles and applications / D. Nasipuri.

Format:

Book

Author/Creator:

Nasipuri, D., author.

Language:

English

Subjects (All):

Stereochemistry.

Physical organic chemistry.

Physical Description:

1 online resource (560 p.)

Edition:

Fourth edition.

Place of Publication:

Kent, [England] : New Academic Science Limited, 2013.

Language Note:

English

Summary:

Subject treated from fundamental and developed to the latest developments. A large cross-section of organic reactions/mechanisms given with stereochemical implications. Relationship between conformation and reactivity specially highlighted. Instrumentation techniques relating to stereochemical investigation discussed in simple language.

Contents:

Cover

Foreword

Preface

Chapter 1 Molecular Geometry and Chemical Bonding

1.1 Introduction

1.2 Molecular structure and chemical bonding

1.2.1 Bond length, bond angle, and dihedral angle

1.2.2 Covalent radii and van der Waals atomic radii

1.3 Hybridisation and Chemical Bonding

1.3.1 Hybridisation and bond angles

1.3.2 Bond angle deformation in small ring compounds

1.4 Hydrogen Bonding

1.5 Rotation around Bonds and Change in Dihedral Angle

1.5.1 Rotation around a single bond

1.5.2 Rotation around a double bond

1.5.3 Restricted rotation around intermediate (hybrid) bonds

1.6 Catenanes

1.7 Summary

References

Chapter 2 Molecular Symmetry and Chirality

2.1 Introduction

2.2 Symmetry Operations and Symmetry Elements

2.2.1 Simple or Proper Axis of Symmetry

2.2.2 Plane of Symmetry

2.2.3 Centre of Symmetry or Inversion Centre

2.2.4 Improper or alternating or rotation-reflection axis

2.3 Point Group Classification

2.4 Molecular Symmetry and Chirality

2.5 Point groups and Symmetry Number

2.6 Summary

Chapter 3 Stereoisomerism: Definitions and Classification

3.1 Introduction

3.2 Molecular Representation

3.3 Classification of Stereoisomers

3.3.1 Classification Based on Symmetry Criterion

3.3.2 Classification Based on Energy Criterion

3.4 Stereoisomerism, Conformation, and Chirality

3.5 Racemic Modifications

3.5.1 Racemic Modifications and Thermodynamic Properties

3.5.2 Classification of Racemic Modifications

3.5.3 Quasi-racemates

3.6 Summary

Chapter 4 Stereoisomerism and Centre of Chirality

4.1 Introduction

4.2 Molecules with a Single Chiral (Stereogenic) Centre

4.2.1 Chiral Manifestations

4.2.2 Molecules with a Tetracoordinate Chiral Centre

4.2.3 Molecules with a Tricoordinate Chiral Centre.

4.3 Configurational Nomenclature

4.3.1 Fischer's D and L nomenclature

4.3.2 R and S nomenclature

4.3.3 R* and S* Nomenclature

4.3.4 CIP Nomenclature of Racemates

4.3.5 Nomenclature of Polysubstituted Cyclanes

4.4 E and Z Nomenclature

4.5 Molecules with a Centre of Chirality and Simple Axes of Symmetry (Cn)

4.6 Molecules With Two and More Chiral Centres

4.6.1 Constitutionally Unsymmetrical Chiral Molecules

4.6.2 Constitutionally Symmetrical Chiral Molecules

4.6.3 Stereoisomerism in Cyclic Compounds

4.7 Summary

Chapter 5 Stereoisomerism : Axial Chirality, Planar Chirality and Helicity

5.1 Introduction

5.2 Principles of Axial and Planar Chirality

5.2.1 Elongated Tetrahedron Approach

5.2.2 Approach Based on Two-dimensional Chiral Simplex

5.3 Stereochemistry of Allenes

5.3.1 Optically active allenes

5.3.2 Configurational Nomenclature

5.4 Stereochemistry of Spiranes and Analogues

5.4.1 Optically Active Alkylidene Cycloalkanes (hemispiranes)

5.4.2 Optically Active Spiranes

5.4.3 Optically Active Adamantoids

5.4.4 Optically Active Catenanes

5.5 Biphenyl Derivatives and Atropisomerism

5.5.1 Optically Active Biphenyl Derivatives

5.5.2 Bridged Biphenyls

5.5.3 Configurational Nomenclature of Biphenyls

5.5.4 Atropisomerism in Compounds other than Biphenyls

5.5.5 Atropisomerism Around sp3-sp3 Bond

5.6 Stereochemistry of Molecules with Planar Chirality

5.6.1 Ansa Compounds

5.6.2 Cyclophanes

5.6.3 Trans-Cycloalkenes

5.7 Helicity

5.8 Miscellaneous Examples of Molecular Stereoisomerism

5.9 Cyclostereoisomerism

5.9.1 Cyclic Directionality of Constitutional Origin

5.9.2 Cyclic Directionality of Conformational Origin

5.9.3 Retro-enantio Isomers

5.10 Summary

Chapter 6 Topicity and Prostereoisomerism.

6.1 Introduction

6.2 Topicity of Ligands and Faces

6.2.1 Homotopic Ligands and Faces

6.2.2 Enantiotopic Ligands and Faces

6.2.3 Diastereotopic Ligands and Faces

6.2.4 Summary of Topic Relationships

6.3 Nomenclature of Stereoheterotopic Ligands and Faces

6.3.1 Symbols for Stereoheterotopic Ligands

6.3.2 Symbols for Stereoheterotopic Faces

6.4 Stereoheterotopic Ligands and NMR Spectroscopy

6.4.1 Diastereotopic Ligands and nmr Spectroscopy

6.4.2 Diastereotopic Faces and NMR Spectroscopy

6.4.3 Diastereotopic Nuclei in Conformationally Mobile Systems

6.4.4 Intrinsic Anisochrony and Conformational Anisochrony

6.4.5 Enantiotopic Nuclei and NMR Spectroscopy

6.4.6 Isogamous and Anisogamous Nuclei

6.5 Prostereoisomerism and Stereoisomerism

6.5.1 Chemical Transformations of Heterotopic Ligands and Faces

6.5.2 Biochemical Transformations of Heterotopic Ligands and Faces

6.6 Summary

Chapter 7 Racemisation and Methods of Resolution

7.1 Introduction

7.2 Mechanisms of Racemisation

7.2.1 Mechanism Involving Carbanions

7.2.2 Mechanism Involving Carbonium Ions

7.2.3 Mechanism Involving Free Radicals

7.2.4 Mechanism Involving Stable Symmetrical Intermediate

7.2.5 Racemisation Through Rotation Around Bonds

7.2.6 Configurational Change in Substitution Reactions

7.3 Asymmetric Transformation and Mutarotation

7.3.1 Mutarotation and First Order Asymmetric Transformation

7.3.2 Second Order Asymmetric Transformation

7.4 Methods of Resolution

7.4.1 Mechanical Separation: Crystallisation Method

7.4.2 Resolution Through the Formation of Diastereomers

7.4.3 Resolution Through The Formation of Molecular Complexes

7.4.4 Resolution by Chromatography

7.4.5 Resolution Through Equilibrium Asymmetric Transformation.

7.4.6 Resolution Through Kinetic Asymmetric Transformation

7.4.7 Resolution by Biochemical Transformation

7.4.8 Resolution Through Inclusion Compounds

7.5 Optical Purity and Enantiomeric Excess

7.5.1 Isotopic Dilution Method

7.5.2 Enzymatic Method

7.5.3 Methods Based on Gas Chromatography

7.5.4 Methods Based on NMR Spectroscopy

7.6 Summary

Chapter 8 Determination of Configuration

8.1 Introduction

8.2 Determination of Absolute Configuration

8.2.1 Method Based on Anomalous X-ray Scattering

8.2.2 Crystals as Probes for the Assignment of Configuration

8.3 Correlative Methods for Configurational Assignment

8.3.1 Chemical Correlation of Configuration

8.3.2 Methods Based on Comparison of Optical Rotation

8.3.3 The Method of Quasi-racemate

8.3.4 Correlative Method Based on NMR Spectroscopy

8.3.5 Correlation Based on Asymmetric Synthesis

8.4 Configuration of Molecules with Axial and Planar Chirality

8.4.1 Configuration of Biphenyls and Analogues

8.4.2 Configuration of Chiral Allenes

8.4.3 Configuration of Alkylidenecycloalkanes

8.4.4 Configuration of Spiranes

8.4.5 Configuration of Trans-cycloalkenes

8.5 Relative Configuration of Diastereomers

8.5.1 Comparison of Physical Properties

8.5.2 Methods Based on NMR Spectroscopy

8.5.3 Chemical Methods

8.5.4 Symmetry Consideration

8.6 Summary

Chapter 9 Conformations of Acyclic Molecules

9.1 Introduction

9.2 Molecular Mechanics and Conformation

9.2.1 Molecular Deformations and Steric Strain

9.2.2 Conformation of Ethane, Propane, and n-butane

9.3 Klyne-prelog Terminology for Torsion Angles

9.4 Physical Methods for Conformational Analysis

9.4.1 Physical and Thermodynamic Properties

9.4.2 Spectroscopic Methods

9.5 Conformations of a Few Acyclic Molecules.

9.5.1 Conformations of Alkanes

9.5.2 Conformations of Halogenoalkanes

9.5.3 Conformation and Intramolecular Hydrogen Bonding

9.5.4 Conformations of 1-Substituted 3, 3-Dimethylbutanes

9.5.5 Conformation Around sp3-sp2 and sp2-sp2 Bonds

9.5.6 Conformations Around carbon-heteroatom bonds

9.6 Diastereomers: Configurations, and Conformations

9.6.1 Diastereomers with two Vicinal Halogens

9.6.2 Diastereomers with two Vicinal Hydroxyl Groups

9.6.3 Diastereomers with Vicinal Hydroxyl and Amino Groups

9.7 Summary

Chapter 10 Conformations of Cyclic Systems: Monocyclic Compounds

10.1 Introduction

10.1.1 Early History

10.2 Conformations of Cyclohexane

10.2.1 Characteristics of the Chair Conformation

10.2.2 Ring Inversion

10.2.3 Stabilisation of the Flexible Conformers

10.3 Conformations of Monosubstituted Cyclohexanes

10.3.1 Transition States and Intermediates

10.3.2 Conformational Free Energy

10.3.3 Isolation and Characterisation of Conformers

10.3.4 Determination of Conformational Free Energy

10.4 Conformations of Di- and Polysubstituted Cyclohexanes

10.4.1 1,1-Disubstituted Cyclohexanes

10.4.2 Disubstituted Cyclohexanes

10.4.3 A Few Atypical Disubstituted Cyclohexanes

10.4.4 Conformation of Polysubstituted Cyclohexanes

10.5 Cyclohexane Ring with One and Two Sp2 Carbons

10.5.1 Cyclohexanone Ring System

10.5.2 Alkylidenecyclohexanes

10.5.3 Cyclohexene

10.5.4 Cyclohexane-1, 4-dione

10.6 Carbocycles Other Than Cyclohexane

10.6.1 Cyclobutane

10.6.2 Cyclopentane

10.6.3 Cycloheptane

10.6.4 Medium rings: Conformations

10.6.5 Medium Rings : Some Unusual Properties

10.6.6 Large Ring Compounds

10.6.7 Rings with Multiple Double Bonds

10.7 Conformational Analysis of Heterocycles

10.7.1 Three-membered Heterocycles.

10.7.2 Four and five-membered Heterocycles.

Notes:

Description based upon print version of record.

Includes bibliographical references at the end of each chapters.

Description based on online resource; title from PDF title page (ebrary, viewed September 8, 2015).

ISBN:

1-78183-057-6

OCLC:

919481096