Basic Organic Stereochemistry

by Eliel, Ernest L.; Wilen, Samuel H.; Doyle, Michael P.

• ISBN13: 9780471374992
• ISBN10: 0471374997
• Edition: 1st
• Format: Paperback
• Copyright: 2001-04-11
• Publisher: Wiley-Interscience

Summary

Stereoisomers are compounds with the same chemical formula and connectivity but with different arrangements of their atoms in 3-dimensional space. Stereochemistry encompasses the study of stereoisomers and their properties. Despite having an identical chemical formula, stereoisomers can have drastically different biological, medicinal, and chemical properties. Basic Organic Stereochemistry explains in clear, concise terms the concepts and properties of stereoisomers. Ideal both as a text for advanced undergraduate or graduate students and as a handy guide for researchers in industry, this superb text covers: Polarimetry and optical rotation Internal coordinates, configuration, and conformation Nature of stereoisomers Barriers between stereoisomers and residual stereoisomers Symmetry operators and symmetry point groups Properties of stereoisomers and stereoisomer discrimination Separation of stereoisomers, resolution, and racemization Suitable for students in organic and biological chemistry, Basic Organic Stereochemistry is unparalleled as a convenient text.

Author Biography

ERNEST L. ELIEL, PhD, is W. R. Kenan Jr. Professor Emeritus at the University of North Carolina, Chapel Hill, North Carolina. He is the coauthor of Stereochemistry of Organic Compounds and the recipient of numerous academic and scientific awards. Professor Eliel is past president of the American Chemical Society and a member of the National Academy of Sciences.

Table of Contents

Preface	xiii
Introduction	1	(7)
Scope	1	(1)
History	1	(4)
Polarimetry and Optical Rotation	5	(3)
References	7	(1)
Structure	8	(22)
Meaning, Factorization, Internal Coordinates, Isomers	8	(3)
Constitution	11	(2)
Configuration	13	(2)
Conformation	15	(2)
Determination of Structure	17	(3)
A Priori Calculation of Structure	20	(5)
Molecular Models	25	(5)
References	26	(4)
Stereoisomers	30	(15)
Nature of Stereoisomers	30	(9)
General	30	(4)
Barriers Between Stereoisomers and Residual Stereoisomers	34	(5)
Enantiomers	39	(1)
Diastereomers	39	(6)
General Cases	39	(3)
Degenerate Cases	42	(2)
References	44	(1)
Symmetry	45	(20)
Introduction	45	(1)
Symmetry Elements	45	(3)
Symmetry Operators and Symmetry Point Groups	48	(10)
Point Groups Containing Chiral Molecules	49	(2)
Point Groups Containing Only Achiral Molecules	51	(7)
Averaged Symmetry	58	(1)
Symmetry and Molecular Properties	59	(6)
Rotation of Polarized Light	59	(2)
Dipole Moment	61	(1)
Symmetry Number	62	(1)
References	63	(2)
Configuration	65	(37)
Definitions: Relative and Absolute Configuration	65	(2)
Absolute Configuration and Notation	67	(8)
Determination of Absolute Configuration	75	(4)
Bijvoet Method	75	(2)
Theoretical Approaches	77	(1)
Modification of Crystal Morphology in the Presence of Additives	77	(2)
Relative Configuration and Notation	79	(5)
Determination of Relative Configuration of Saturated Aliphatic Compounds	84	(14)
X-Ray Structure Analysis	85	(1)
Chemical Interconversion Not Affecting Bonds to the Stereogenic Atom	86	(1)
Methods Based on Symmetry Considerations	86	(3)
Correlation Via Compounds with Chiral Centers of Two Types	89	(1)
The Method of Quasi-Racemates	90	(1)
Chemical Correlations Affecting Bonds to a Chiral Atom in a ``Known'' Way (For an Overview, see ref. 32.)	90	(5)
Correlation by Stereoselective Synthesis of ``Known'' Stereochemical Course	95	(3)
Chiroptical, Spectroscopic, and Other Physical Methods	98	(1)
Conclusion: Network Arguments	98	(4)
References	98	(4)
Properties of Stereoisomers and Stereoisomer Discrimination	102	(95)
Introduction	102	(1)
Stereoisomer Discrimination	102	(4)
The Nature of Racemates	106	(2)
Properties of Racemates and of Their Enantiomer Components	108	(34)
Introduction	108	(1)
Optical Activity	109	(1)
Crystal Shape	109	(1)
Density and Racemate Type	110	(1)
Melting Point	111	(4)
Solubility	115	(4)
Vapor Pressure	119	(1)
Infrared Spectra	120	(1)
Electronic Spectra	121	(1)
Nuclear Magnetic Resonance Spectra	122	(1)
X-Ray Spectra	123	(1)
Liquid State and Interfacial Properties	124	(4)
Chromatography	128	(1)
Mass Spectrometry	129	(1)
Interaction with Other Chiral Substances	130	(2)
Biological Properties	132	(6)
Origins of Enantiometric Homogeneity in Nature	138	(4)
Determination of Enantiomer and Diastereomer Composition	142	(55)
Introduction	142	(3)
Chiroptical Methods	145	(2)
NMR Methods Based on Diastereotopicity	147	(13)
Chromatographic and Related Separation Methods Based on Diastereomeric Interactions	160	(16)
Kinetic Methods	176	(2)
Miscellaneous Methods	178	(2)
References	180	(17)
Separation of Stereoisomers, Resolution, and Racemization	197	(106)
Introduction	197	(1)
Separation of Enantiomers by Crystallization	198	(11)
Crystal Picking and Triage	198	(1)
Conglomerates	198	(3)
Preferential Crystallization	201	(3)
Asymmetric Transformation of Racemates and Total Spontaneous Resolution	204	(5)
Chemical Separation of Enantiomers via Diastereomers	209	(44)
Formation and Separation of Diastereomers: Resolving Agents	209	(18)
Resolution Principles and Practice	227	(4)
Separation Via Complexes and Inclusion Compounds	231	(5)
Chromatographic Resolution	236	(4)
Asymmetric Transformations of Diastereomers	240	(6)
General Methods for the Separation of Diastereomers	246	(7)
Enantiometric Enrichment and Resolution Strategy	253	(4)
Kinetic Resolution	257	(17)
Theory and Stoichiometric and Abiotic Catalytic Kinetic Resolution	258	(10)
Enzymatic Resolution	268	(6)
Miscellaneous Separation Methods	274	(3)
Racemization	277	(26)
Racemization Processes	278	(6)
Racemization of Amino Acids	284	(3)
References	287	(16)
Heterotopic Ligands and Faces: Prostereoisomerism and Prochirality	303	(36)
Introduction and Terminology	303	(2)
Significance and History	305	(2)
Homotopic and Heterotopic Ligands and Faces	307	(11)
Homotopic Ligands and Faces	307	(3)
Enantiotopic Ligands and Faces	310	(2)
Diastereotopic Ligands and Faces	312	(3)
Concepts and Nomenclature	315	(3)
Heterotopicity and Nuclear Magnetic Resonance	318	(11)
General Principles. Anisochrony	318	(2)
NMR in Assignment of Configuration and of Descriptors of Prostereoisomerism	320	(3)
Origing of Anisochrony	323	(2)
Conformationally Mobile Systems	325	(4)
Heterotopic Ligands and Faces in Enzyme-Catalyzed Reactions	329	(10)
Heterotopicity and Stereoelective Synthesis	329	(1)
Heterotopicity and Enzyme-Catalyzed Reactions	330	(5)
References	335	(4)
Stereochemistry of Alkenes	339	(37)
Structure of Alkenes and Nature of cis-trans Isomerism	339	(9)
General	339	(1)
Nomenclature	340	(2)
Cumulenes	342	(1)
Alkenes with Low Rotational Barriers and Nonplanar Alkenes	342	(4)
The C=N and N=N Double Bonds	346	(2)
Determination of Configuration of cis-trans Isomers	348	(14)
Chemical Methods	348	(5)
Physical Methods	353	(9)
Interconversion of cis-trans Isomers: Position of Equilibrium and Methods of Isomerization	362	(14)
Position of cis-trans Equilibria	362	(4)
Methods of Equilibration	366	(2)
Directed cis-trans Interconversion	368	(3)
References	371	(5)
Conformation of Acyclic Molecules	376	(45)
Conformation of Ethane, Butane, and Other Simple Saturated Acyclic Molecules	376	(12)
Alkanes	376	(7)
Saturated Acyclic Molecules with Polar Substituents or Chains and the Anomeric Effect	383	(5)
Conformation of Unsaturated Acyclic and Miscellaneous Compounds	388	(10)
Unsaturated Acyclic Compounds	388	(7)
Alkylbenzenes	395	(2)
Miscellaneous Compounds	397	(1)
Physical and Spectral Properties of Diastereomers and Conformers	398	(9)
General	398	(1)
Dipole Moments	399	(1)
Infrared Spectra	400	(1)
NMR Spectroscopy	401	(6)
Conformation and Reactivity: The Winstein-Holness Equation and the Curtin-Hammett Principle	407	(14)
References	415	(6)
Configuration and Conformation of Cyclic Molecules	421	(113)
Stereoisomerism and Configurational Nomenclature of Ring Compounds	421	(2)
Determination of Configuration of Substituted Ring Compounds	423	(6)
Introduction	423	(1)
Symmetry-Based Methods	424	(1)
Methods Based on Physical and Chemical Properties	425	(2)
Correlation Methods	427	(2)
Stability of Cyclic Molecules	429	(7)
Strain	429	(3)
Ease of Cyclization as a Function of Ring Size	432	(1)
Ease of Ring Closure as a Function of the Ring Atoms and Substituents: The Thorpe-Ingold Effect	433	(1)
Baldwin's Rules	434	(2)
Conformational Aspects of the Chemistry of Six-Membered Ring Compounds	436	(44)
Cyclohexane	436	(3)
Monosubstituted Cyclohexanes	439	(8)
Disubstituted and Polysubstituted Cyclohexanes	447	(6)
Conformation and Physical Properties in Cyclohexane Derivatives	453	(4)
Conformation and Reactivity in Cyclohexanes	457	(6)
sp2 Hybridized Cyclohexyl Systems	463	(9)
Six-Membered Saturated Heterocycles	472	(8)
Chemistry of Ring Compounds Other than Six-Membered Ones	480	(11)
Three-Membered Rings	480	(1)
Four-Membered Rings	481	(1)
Five-Membered Rings	482	(3)
Rings Larger Than Six-Membered	485	(6)
Stereochemistry of Fused, Bridged, and Caged Ring Systems	491	(43)
Fused Rings	492	(9)
Bridged Rings	501	(4)
Propellanes	505	(1)
Catenanes, Rotaxanes, Knots, and Mobius Strips	505	(8)
Cubane, Tetrahedrane, Didecahedrane, Adamantane, and Buckminsterfullerene	513	(4)
References	517	(17)
Chiroptical Properties	534	(74)
Introduction	534	(1)
Optical Activity and Anisotropic Refraction	535	(9)
Origin and Theory	535	(6)
Optical Rotatory Dispersion	541	(3)
Circular Dichroism and Anisotropic Absorpation	544	(4)
Applications of Optical Rotary Dispersion and Circular Dichroism	548	(37)
Determination of Configuration and Conformation: Theory	548	(2)
Classification of Chromophores	550	(3)
Sector and Helicity Rules	553	(14)
Excition Chirality	567	(3)
Other Applications: Induced ORD and CD	570	(6)
Circular Dichroism of Chiral Polymers	576	(9)
Applications of Optical Activity	585	(12)
Polarimetry	585	(8)
Empirical Rules and Correlations: Calculation of Optical Rotation	593	(4)
Vibrational Optical Activity	597	(11)
References	598	(10)
Chirality in Molecules Devoid of Chiral Centers	608	(41)
Introduction and Nomenclature	608	(3)
Allenes	611	(6)
Historical Overview and Natural Occurrence	611	(1)
Synthesis of Optically Active Allenes	612	(1)
Determination of Configuration and Enantiomeric Purity of Allenes	613	(3)
Cyclic Allenes, Cumulenes, and Ketene Imines	616	(1)
Alkylidenecycloalkanes	617	(3)
Spiranes	620	(2)
Biphenyls and Atropisomerism	622	(10)
Introduction	622	(1)
Biphenyls and Other Atropisomers of the sp2-sp2 Single-Bond Type	623	(6)
Atropisomerism About sp2-sp3 Single Bonds	629	(1)
Atropisomerism About sp3-sp3 Bonds	630	(2)
Molecular Propellers	632	(4)
Helicenes	636	(2)
Molecules with Planar Chirality	638	(11)
Introduction	638	(1)
Cyclophanes	639	(1)
trans-Cycloalkenes	640	(2)
Metallocenes and Related Compounds	642	(1)
References	642	(7)
Index	649