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Stereochemistry
Stereochemistry
A Three-Dimensional Insight
ANIL V. KARNIK
Department of Chemistry, University of Mumbai,
Mumbai, Maharashtra, India
MOHAMMED HASAN
Department of Chemistry, University of Mumbai,
Mumbai, Maharashtra, India
Elsevier
Radarweg 29, PO Box 211, 1000 AE Amsterdam, Netherlands
The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom
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Contents
About the authors xvii

Foreword xix
Preface xxiii
Part I Fundamentals of stereochemistry

1. Basic concepts of structure and stereochemistry 3
1.1 Introduction 3
1.2 A brief history 5
1.3 Molecular geometry 5
1.3.1 Van der Waals’ radius 6
1.3.2 Bond length 7
1.3.3 Bond angle 7
1.3.4 Dihedral angle 8
1.4 Isomers 9
1.4.1 Conformational isomers 10
1.4.2 Configuration and configurational isomers 11
1.5 Projection formulae 13
1.5.1 Fischer projection 13
1.5.2 Newman projection 15
1.5.3 Sawhorse projection 15
1.5.4 Inter-conversion of Fischer projection to Newman projection or
Sawhorse projection 16
1.5.5 Flying wedge/zig-zag projection formula 16
1.5.6 Inter-conversion of Fischer projection and zig-zag projection 18
1.6 Summary 20
Questions and problems 21
References 23
2. Symmetry and point groups 25

2.1 Introduction 25
2.2 Symmetry elements and symmetry operations 27
2.2.1 Simple or proper axis of symmetry (Cn) and proper rotational
operations ðCnk Þ 27
2.2.2 Plane of symmetry (σ) Operation of reflection (σ) 29
2.2.3 Centre of symmetry (i) Operation of inversion (i) 30
2.2.4 Alternating or rotation-reflection axis of symmetry (Sn) 32
v
vi Contents
2.3 Point groups and their classification 33

2.3.1 Linear molecules with high symmetry (Special group) 34
2.3.2 Nonlinear molecules with high symmetry and molecules with
platonic group structures 35
2.3.3 Nonlinear molecules with high Cn axis (without platonic group
molecules) 37
2.3.4 Nonlinear molecules with absence of Cn, axis n $ 2 39
2.4 The chiral compounds and the difference between asymmetry and
dissymmetry 39
2.5 Symmetry number (σ) 41
2.5.1 Practical method to assign the point group of given organic
compound 43
2.6 Summary 44
References 48
3. Elements of chirality and chiral stereoisomerism 49

3.1 Introduction 49
3.2 Molecules with central chirality 49
3.2.1 Configurational descriptors for molecules with central chirality 52
3.3 Molecules with two or more chiral centres 56
3.3.1 Constitutionally unsymmetrical chiral molecules 57
3.3.2 Stereoisomerism in constitutionally symmetrical chiral molecules 62
3.3.3 Stereoisomerism in cyclic molecules 64
3.4 Molecules with the presence of chiral axis 66
3.4.1 Assignment of configurational descriptors to molecules with
presence of chiral axis 68
3.4.2 Allenes 68
3.4.3 Alkylidene cycloalkanes/Hemispiranes 69
3.4.4 Spiranes 70
3.4.5 Atropisomerism 71
3.4.6 Atropisomerism of biaryls, restricted rotation around sp2-sp2, CC
bond 73
3.4.7 Assignment of configurational descriptors to chiral biphenyls 75
3.4.8 Bridged biphenyls 76
3.5 Planar chirality 77
3.5.1 Assignment of configurational descriptor to molecules with chiral
plane 79
3.5.2 Cyclophanes and ansa compounds 79
3.5.3 Trans-cyclooctene 80
Contents vii
3.5.4 Chiral ferrocenes 81

3.6 Helicity 82
3.7 Cyclostereoisomerism 83
3.8 Summary 85
References 90
Part II Enantiomer properties

4. Chiroptical properties: Origin and applications 95
4.1 Introduction 95
4.2 Optical activity 97
4.2.1 Origin of the optical activity 98
4.2.2 Circular birefringence 99
4.2.3 Dissymmetric compounds and optical activity 101
4.2.4 Circular dichroism 102
4.3 Optical rotatory dispersion curves (ORD) 104
4.3.1 Cotton effect curves 104
4.3.2 The Cotton effect circular dichroism and optical rotatory
dispersion curves 106
4.3.3 Applications of the plain optical rotatory dispersion curves 106
4.3.4 Applications of the Cotton effect optical rotatory
dispersion/circular dichroism curves 107
4.3.5 Empirical and semiempirical rules for conformational and
configurational studies 110
4.4 The axial α-haloketone rule and its applications 111
4.5 Octant rule 114
4.5.1 Applications of the octant rule 115
4.6 Inherently symmetric or inherently dissymmetric optically active
chromophores 117
4.7 Helicity rules for inherently chiral chromophores 118
4.7.1 α, β-Unsaturated ketone or enone 118
4.7.2 1,3-Conjugated dienes 119
4.7.3 Biaryls 119
4.7.4 Helicenes 119
4.8 Lowe’s rule for allenes 120
4.9 Exciton coupling and dibenzoate chirality rule 120
4.10 Summary 123
References 125
viii Contents
5. Configurational analysis 129

5.1 Introduction 129
5.2 Methods for the determination of absolute configuration 130
5.2.1 Basic terminology of resonant X-ray scattering 130
5.2.2 Determination of absolute configuration using resonant X-ray
scattering 132
5.2.3 Determination of absolute configuration by use of crystalline
sponge-X-ray diffraction method 133
5.2.4 Crystal morphological changes for assignment of absolute
configuration 135
5.2.5 Determination of absolute configuration using chiroptical
methods 139
5.3 Correlative methods for determination of configurations 140
5.3.1 Chemical correlative methods of determination of configurations 140
5.3.2 Correlative methods based on comparison of optical rotations 146
5.3.3 Quasi-racemate formation between two different molecules 151
5.3.4 NMR methods 155
5.4 Assignment of configuration based on asymmetric synthesis 159
5.4.1 Cram’s rule 160
5.4.2 Prelog’s rule 163
5.4.3 Sharpless asymmetric epoxidation 164
5.5 Horeau’s method of assignment of configuration based on kinetic
resolution 165
5.6 ‘Stand-alone’ methods for determination of configuration 166
5.6.1 Assignment of configuration to an alkylidenecycloalkane via
stereoselective synthesis 167
5.6.2 Assignment of absolute configuration to (-)-trans-cyclooctene 167
5.6.3 Determination of absolute configuration of allenes 169
5.6.4 Assignment of absolute configuration to a spiro compound 170
5.6.5 Assignment of absolute configuration to a biphenyl derivative 171
5.7 Methods to distinguish between configurations of diastereoisomers 171
5.7.1 Auwer’s Skita rule 172
5.7.2 UV-vis spectroscopy 173
5.7.3 IR spectroscopy 173
5.7.4 X-ray diffraction studies 174
5.7.5 NMR spectroscopy 174
5.8 Chemical method 177
5.9 Summary 178
References 183
Contents ix
6. Racemates: Properties and methods of resolution 187

6.1 Introduction: Properties of enantiomers and racemates 187
6.1.1 Melting point phase diagrams 188
6.1.2 Crystal shape/morphology 189
6.1.3 Density of racemic modifications in solid state 191
6.1.4 Solubility behaviour of racemic modifications 192
6.1.5 IR spectroscopy 192
6.1.6 NMR spectroscopy 192
6.1.8 Chromatographic behaviour 193
6.1.9 Vapour pressure 194
6.2 Resolution of racemates 195
6.2.1 Resolution of racemic modification exhibiting conglomerate
behaviour: Spontaneous crystallisation 195
6.2.2 Formation of diastereomeric salts or compounds followed by
preferential crystallisation 196
6.2.3 Resolution though formation of diastereomeric complexes 202
6.2.4 Chromatographic resolutions 203
6.2.5 Resolution of racemates via equilibrium asymmetric
transformation 205
6.2.6 Kinetic resolutions of racemates 208
6.2.7 Dynamic kinetic resolutions 211
6.3 Racemisation processes 213
6.3.1 Formation of a resonance stabilized carbanions 214
6.3.2 Involvement of tautomeric species 214
6.3.3 Racemisations involving a stable carbocation intermediate 214
6.3.4 Racemisations involving a stable carbon-free radical intermediate 215
6.3.5 Opposite reactions occurring simultaneously 215
6.3.6 Racemisation encountered in DKR 216
6.3.7 Rotation around single bond 216
6.4 Summary 216
References 219
Part III Conformations and conformational analysis

7. Conformation of acyclic molecules 227
7.2 Conformation 228
x Contents
7.2.1 Torsional strain 228

7.2.2 Notations for torsion angle, the KlynePrelog method 229
7.3 Estimating strain energy 232
7.3.1 Cause of the potential energy barriers 233
7.4 Study of conformations due to rotation about sp3sp3 single bond 235
7.4.1 Rotations around CC bond 235
7.4.2 Alkanes with polar substituents 240
7.4.3 Rotation around CN single bond 241
7.4.4 Rotation around CP single bond 242
7.4.5 Rotation around CO single bond 243
7.4.6 Conformations due to rotation around sp3sp2 single bond 244
7.4.7 Conformations due to rotation around sp2sp2 single bond 246
7.5 Spectral/analytical/theoretical means of internal rotation studies 247
7.5.1 Molecular mechanics and quantum mechanical approaches to
estimate energies of molecules in different arrangements 247
7.5.2 Dipole moment 248
7.5.3 Use of NMR and ESR techniques 249
7.5.4 Microwave spectroscopy 250
7.5.5 Electron diffraction studies 251
7.5.7 Infrared and Raman spectroscopy 252
7.6 Conformation and chemical reactivity 253
7.6.1 CurtinHammett principle 255
7.6.2 Effect of conformation on kinetic and/or stereochemical
outcome of chemical reactions 259
7.7 Summary 265
References 269
8. Conformations of cyclic, fused and bridged ring molecules 273

8.2 Cyclohexane conformations 275
8.2.1 The chair conformation 275
8.2.2 Ring inversion in cyclohexane 279
8.2.3 Nonchair conformations of cyclohexane 282
8.2.4 Cyclohexane derivatives with two or more substituents 286
8.3 Cyclohexanone conformational analysis 295
8.4 Alkylidenecyclohexane conformation 297
8.5 Cyclohexene conformation 298
8.6 Cyclopropane conformation 300
Contents xi
8.7 Cyclobutane conformations 300

8.8 Normal ring compounds 301
8.8.1 Cyclopentane conformation 301
8.8.2 Cycloheptane conformation 302
8.9 Medium-sized carbocycles 302
8.9.1 Cyclooctane conformations 303
8.9.2 Cyclononane conformations 304
8.9.3 Cyclodecane conformations 305
8.10 Large ring carbocycles 306
8.11 Size and conformation-based trends in alicyclic compounds 307
8.11.1 Accommodation of anti butane unit 307
8.11.2 Accommodation of trans double bond 307
8.11.3 Transannular effects 308
8.11.4 I-strain concept 314
8.12 Components of heterocyclic rings conformations 314
8.12.1 Ring Inversion barriers in heterocycles 316
8.12.2 Pyramidal inversion 317
8.12.3 Anomeric effect 318
8.12.4 Intramolecular hydrogen bonding 322
8.12.5 1,3-Syn-axial interactions 322
8.13 Fused ring compounds 323
8.13.1 Decalins or bicyclo[4.4.0]decane 325
8.13.2 Cis-decalin 325
8.13.3 Trans-decalin 327
8.14 Introduction of angular methyl groups in cis and -trans-decalins 328
8.15 The octahydronaphthalene or octalins 329
8.16 Bicyclo[4.3.0]nonane or hydrindane 330
8.17 Bicyclo[3.3.0]octane or octahydropentalene 332
8.18 Fused polycyclic compounds 332
8.18.1 Perhydrophenanthrene 333
8.18.2 Perhydroanthracenes 336
8.18.3 Steroids stereochemistry 338
8.19 Bridged-ring compounds 340
8.19.1 Bicyclo[1.1.1]pentane 340
8.19.2 Bicyclo[2.1.1]hexane 341
8.19.3 Bicyclo[2.2.1]heptane 342
8.19.4 Bicyclo[2.2.2]octane 344
8.19.5 Bicyclo[3.2.1]octane 344
8.19.6 Bicyclo[3.3.1]nonane 345
xii Contents
8.19.7 Tricyclo[1.1.1.0]pentane or [1.1.1]propellane 345

8.19.8 Adamantane or tricyclo[3.3.1.13,7]decane 345
8.19.9 The bicyclo[2.2.1]heptyl and bicyclo[2.2.2]octyl systems and
their contribution to nonclassical carbocation concept 345
8.19.10 Bredt’s rule 348
8.20 Conformation and chemical reactivity of cyclic compounds 349
8.20.1 Reactions influenced by steric effects 351
8.20.2 Systems where equatorially substituted conformer reacts faster 352
8.20.3 Systems where axially substituted conformer reacts faster 353
8.20.4 Reactions where stereo-electronic effects operate 355
8.20.5 Molecular rearrangements 358
8.21 Summary 363
References 368
Part IV Stereochemical reactivity

9. Prochirality 379
9.2 Topicity, the relationship between two or more homomorphic
ligands and faces 381
9.2.1 Homotopic ligands and faces 382
9.3 Nomenclature system for stereoheterotopic ligands 389
9.3.1 Stereodescriptors for enantiotopic ligands 390
9.3.2 Diastereotopic ligands at pro-pseudoasymmetric centre 392
9.3.3 Stereodescriptors for diastereotopic ligands 393
9.3.4 Enantiotopic ligands in molecules with pro-chiral axis 394
9.3.5 Enantiotopic ligands in molecules with pro-chiral plane 395
9.3.6 Stereo-heterotopic ligands in molecules with pro-stereogenic
units other than pro-chiral units 396
9.3.7 Stereodescriptors for enantiotopic faces 396
9.3.8 Stereodescriptors for diastereotopic faces 397
9.4 Discrimination/recognition of stereo-heterotopic ligands and faces
by bio-catalysts 398
9.5 Discrimination/recognition of stereo-heterotopic ligands and faces
by chiral chemical reagents/catalysts 398
9.6 Recognition of stereo-heterotopic ligands by NMR 400
9.7 Summary 401
References 405
Contents xiii
10. Diastereomeric transition states and stereoselectivity 407

10.2 Stereoselective processes 407
10.2.1 Stereospecific reactions 408
10.2.2 Asymmetric synthesis 411
10.2.3 Steric and conformational effects in stereoselective processes 414
10.3 The Asymmetric Aldol condensation reaction 417
10.3.1 Substrate-controlled Aldol reactions 420
10.3.2 Chiral reagent (enolate) controlled Aldol reactions 420
10.3.3 Double stereo-differentiation 421
10.4 Sharpless epoxidation 422
10.5 Jacobsen-Katsuki epoxidation 426
10.6 Asymmetric dihydroxylation (AD) 427
10.7 Asymmetric aminohydroxylation (AA) 430
10.8 Enantioselective reduction of pro-chiral carbonyl compounds 433
10.8.1 Chiral LiAlH4 reagents 433
10.8.2 Enantioselective reduction of prochiral ketones using
BINAL-H 434
10.8.3 Chiral borane reagents for enantioselective reductions of
prochiral ketones 435
10.8.4 Enantioselective reductions of functionalised carbonyl
compounds using Ru-BINAP catalyst 438
10.9 Homogeneous asymmetric catalytic reductions of prochiral alkene
derivatives 440
10.10 Allylamine to enamine asymmetric isomerisation 443
10.11 Enantioselective reduction of C 5 N moiety via chiral cyclic hydrazone,
synthesis of α-amino acids 445
10.12 Asymmetric Diels-Alder reaction 445
10.12.1 Chiral dienophiles for asymmetric Diels-Alder reaction 446
10.12.2 Chiral dienes for asymmetric Diels-Alder reaction 448
10.12.3 Chiral catalysts in asymmetric Diels-Alder reactions 449
10.13 Chiral organo-catalysis 449
10.14 Summary 453
References 457
Further reading 463
11. Chiral analytical chemistry 465

11.2 Chiral analysis terminology 467
xiv Contents
11.3 Chiroptical methods for determination of enantiomer composition 469

11.4 NMR for determination of enantiomer composition 470
11.4.1 Chiral derivatising agents for determination of enantiomer
composition 470
11.4.2 Chiral solvating agents for determination of enantiomer
composition 475
11.4.3 Chiral shift reagents for determination of enantiomer
composition 476
11.5 Chromatographic techniques for determination of enantiomer
composition 479
11.5.1 Chiral derivatising agents for the indirect gas chromatography
method 481
11.5.2 Chiral derivatising agents for the indirect high-performance
liquid chromatography method 482
11.5.3 Use of chiral stationary phase (CSP) for determination of
enantiomer composition 483
11.5.4 Use of chiral mobile phase for determination of enantiomer
composition 487
11.6 Use of capillary electrophoresis for determination of enantiomer
composition 487
11.7 Enantiomer recognition and evaluation of chiral sensors 489
11.7.1 Basics of chiral recognition and optical responses 490
11.7.2 Ultraviolet spectroscopybased chirality sensor 492
11.7.3 Fluorescence spectroscopybased chirality sensor 495
11.7.4 Circular dichroism (CD) spectroscopybased chirality sensor 497
11.7.5 Determination of host-guest stoichiometry 498
11.7.6 Determination of binding constant 501
11.7.7 BenesiHildebrand method 503
11.7.8 SternVolmer method 503
11.8 Summary 506
References 509
12. Pericyclic reactions 515

12.2 The atomic orbitals and the molecular orbitals 516
12.3 The conservation of symmetry approach or the correlation diagram
approach 523
12.3.1 Correlation diagram method for electrocyclic reactions 524
12.3.2 Correlation diagram for the cyclo-addition reactions 528
12.4 The frontier molecular orbitals approach 530
Contents xv
12.4.1 Application of FMO approach to cyclo-addition reactions 530

12.4.2 The FMO approach for the electrocyclic reactions 533
12.4.3 The application of FMO approach to sigmatropic
rearrangements 536
12.5 The rates of Diels-Alder reactions 541
12.6 Role of coefficients on selectivity 544
12.7 1,3-Dipolar cycloaddition reactions 545
12.8 Summary 546
References 549
Solutions and keys to the problems 551

Index 575
About the authors
Prof. Anil V. Karnik worked as a Professor of Organic Chemistry and

the Head of Department of Chemistry, University of Mumbai, India and
retired in 2018. Presently, he works as a UGC-BSR Fellow at the
Department of Chemistry, University of Mumbai. He has taught
stereochemistry-related topics to postgraduate students for more than 30
years. He has delivered hundreds of lectures on various aspects of stereo-
chemistry at different state universities and colleges across India. His
research area includes various fundamental aspects of stereochemistry,
which has resulted in quality publications in standard international jour-
nals; he has two reviews and a chapter in a book to his credit. His research
areas include enantioselective synthesis, chiral organocatalysis, synthesis of
sterically crowded biaryl and helical molecules, chiral supramolecular
chemistry, conformational analysis, and nonenzymatic kinetic resolutions.
Dr. Mohammed Hasan graduated with a PhD in Organic Chemistry

from the University of Mumbai, working with Prof. Anil V. Karnik on
the topic ‘Studies in Chiral Molecular Recognition’. Post PhD, he began
his career as a research scientist in pharmaceutical industry CIPLA Ltd.,
working on synthesis of complex, chiral anticancer drug molecules. Later,
he went on to gain significant international postdoctoral research experi-
ence in Europe and China, working on various synthetic and supramolec-
ular chemistry aspects of stereochemistry. His research interest includes
synthetic organic chemistry, chirality, supramolecular chemistry, optical
methods, and green chemistry. He has many publications in high impact
factor international journals. Currently, he is a Senior Scientist in industry
and a visiting researcher at the Department of Chemistry, University of
Mumbai.
Anil V. Karnik and Mohammed Hasan
Department of Chemistry, University of Mumbai, Mumbai, Maharashtra, India
xvii
Foreword
Stereochemistry is the most stimulating and important topic for any

organic chemist, including theoretical chemists, to learn. The standard ref-
erence textbook on the subject is ‘Stereochemistry of Organic
Compounds’ by Eliel and Wilen, where many topics are presented in the
form of mini-reviews. Some other textbooks on stereochemistry have
been made available by many authors.
Stereochemistry requires visualisations of three-dimensional interac-
tions, understanding of various notations, definitions, and terminologies
with clarity. This book by Prof. Karnik and Dr. Hasan has presented the
fundamental aspect of stereochemistry with illustrative figures and recent
examples, without which, topics such as symmetry elements and point-
groups, conformational analysis, and stereo-electronic effects cannot be
understood with sufficient clarity. Undergraduate and graduate students
need a textbook with fundamental aspects with authentic (like IUPAC
terminology) information.
A configurational assignment has been a daunting task in stereochemis-
try. Single crystal X-ray diffraction method has occupied a centre stage in
configurational assignment, which needs a good thorough understanding.
Single crystal X-ray analysis along with spectral interpretations is posed to
replace some of yesteryear’s methods like chemical or optical correlative
methods. A comparatively different method such as configurational assign-
ment based on crystal morphological changes is a newer addition at the
textbook level. It is imperative that the lesser used methods are slowly
phased out from the undergraduate and graduate studies and newer and
more frequently used methods are introduced to our students. This pres-
ent book is a positive step in that direction.
Factors affecting conformations have been illustrated with
suitable examples. Computational methods are being used more fre-
quently to estimate conformational aspects and to estimate interactions
between two or more species in the recent literature. The graduate-level
students and research students need an empirical understanding of these
methods without resorting to mathematical treatment, and the discussion
provided in the book has been largely successful in this regard.
Selectivity is the heart of organic synthesis. Stereoselectivity is among
the most delicate of the various selectivity components that an organic
xix
xx Foreword
chemist deals with. This has been presented with recent and more rele-
vant examples. The expanse of asymmetric synthesis cannot be covered in
a textbook of this type. But the idea about the important approaches pos-
sible has been well-illustrated as a part of the foundation towards planning
asymmetric synthesis.
The significant use of chiral analytical chemistry is increasing in aca-
demic institutes and the pharmaceutical industry. The fundamentals of
enantiomer composition analysis have been provided in sufficient detail.
Many research laboratories report binding constants in supramolecular
interactions as a part of chiral supramolecular studies, these methods have
been illustrated adequately, which should be helpful to research students
as well.
Pericyclic reactions present a rather different type of approach in
organic synthesis. Basic stereoselectivity principles of pericyclic reactions
have been presented with helpful figures. The importance of coefficients
of molecular orbitals, in governing product selectivity or the effect of sub-
stituents on energies of Highest energy electron Occupied Molecular
Orbital Lowest energy electron Unoccupied Molecular Orbital and
hence the rates of D A reactions, have been discussed, which usually is
lacking in pericyclic topic presented in stereochemistry textbooks.
Chapter 4, Chiroptical properties: Origin and applications on chiropti-
cal properties also discusses many aspects which generally do not find a
place in stereochemistry textbooks. The origin of optical activity, the cir-
cular birefringence or the circular dichroism have been presented in an
effective manner. Discussion on conformationally crowded molecules
with twisted chromophores, inherently dissymmetric chromophores, exhi-
biting high optical rotations should be interesting to the earnest student of
the subject.
All the chapters provide relevant references of original articles, reviews,
and some specialised books on the topic. The present textbook on stereo-
chemistry presents all essential and important concepts with clarity and
provides up-to-date information on almost all aspects of stereochemistry
for undergraduate and graduate students of chemistry. It becomes apparent
that the book has the basic objective of bringing the subject clarity, with-
out compromising on the most essential concepts, but avoiding less-
frequently encountered components. This book should be successful in
developing ‘fondness’ for stereochemistry amongst the student commu-
nity. It should be useful to the chemistry academic faculty and industrial
Foreword xxi
chemists equally. It is a much-welcomed addition to the repertoire of

practicing researchers and academics.
The academic and research backgrounds of the authors justify their
book on stereochemistry.
Ganesh Pandey
Department of Chemistry, Institute of Science,
Banaras Hindu University, Varanasi, India
Preface
This book has been written for the undergraduate/postgraduate and

research students of chemistry and biochemistry. Further, it supports the
academic community and practicing researchers in the chemical and phar-
maceutical industries worldwide.
Understanding in-depth chemistry without considering stereochemical
aspects is practically impossible. Physical properties and spectral properties
of molecules are governed by the molecular geometries as well as the
intra- and intermolecular interactions, where two-dimensional considera-
tions are not sufficient, in most cases. The three-dimensional considera-
tions become even more relevant when chemical transformations are in
the picture. Unusual selectivity observed in certain types of reactions,
seemingly different functional group chemistry observed in different sub-
strates having the same functional group and same reaction conditions,
abnormally fast reactions or ‘no reaction’ in certain cases, biochemical pre-
ferences for a particular isomer, all these puzzles can be delineated by
applications of stereochemical principles.
The book by Eliel and Wilen, with contribution from Mander, con-
tinues as a stereochemistry reference book for the majority of the aca-
demic and research community for quite some time. The books by Prof.
Nasipuri and Prof. Nogardi have provided additional options on the sub-
ject coverage. There are a few other good books available on the topic.
Some of the books published over the last two decades, address some
components with clarity but leave out other important topics. We felt
that the time had come to make an up-to-date textbook on stereochemis-
try that would include discussions on all essential topics in a comprehen-
sive yet coherent manner, a perfect combination for the students. Specific
attention has been paid to the development of the stereochemistry con-
cepts among the readers through simplified language text and self-
explained figures and various highlighted structures.
Fundamental considerations of three-dimensional chemistry, the ste-
reochemistry, remain largely unchanged. However, some newer develop-
ments in each of the subareas of stereochemistry, such as conformational
analysis and configurational determination, have occurred. Literature
shows a larger dependence on computational methods, in discussion on
conformational aspects and in studies related to interactions between
xxiii
xxiv Preface
different species. More clarity has emerged in understanding the reactivity

influenced by conformational aspects and stereoselectivity components.
Chiral analytical chemistry has also become an indispensable area.
Determination of configuration, an essential component of stereochemis-
try, has seen some older methods becoming obsolete and some newer
methods emerging recently.
This book has been divided into four sections, comprising
‘Fundamentals of Stereochemistry’ (Part-I), ‘Enantiomer Properties’
(Part-II), ‘Conformations and Conformational Analysis’ (Part-III) and
‘Stereochemical Reactivity’ (Part-IV).
Part I: ‘Fundamentals of Stereochemistry’, consists of three chapters
focusing on Basic Concepts of Structure and Stereochemistry, Symmetry
and Point Groups and Elements of Chirality and Chiral Stereoisomerism.
The part on fundamentals of stereochemistry presents the geometrical
parameters such as bond length, bond angle, and dihedral angle. The sym-
metry elements and point group with a focus toward chirality has been
provided in the section. The existence of different elements of chirality
and methods of assignment of configurational descriptors have been pro-
vided in this section.
Part II: ‘Enantiomer properties’, also contains three chapters namely
Chiroptical Properties: Origin and Application; Configurational Analysis
and Racemates: Properties and Methods of Resolution. It discusses the
chiroptical properties, origin of optical activity and components associated
with the same. Determination of configuration and resolution of race-
mates have been provided in this section.
Part III: ‘Conformations and Conformational Analysis’, covers two
major chapters focusing on Conformation of Acyclic Molecules, and
Conformations of Cyclic, Fused and Bridged Ring Molecules with recent
updates. It provides an exhaustive discussion on conformational analysis of
acyclic, cyclic molecules, fused ring compounds and bridged ring com-
pounds. Conformation-dependent reactivity of molecules has been dis-
cussed with many suitable examples.
Part IV: ‘Stereochemical reactivity’, includes four chapters, namely
Prochirality, Diastereomeric Transition States and Stereoselectivity, Chiral
Analytical Chemistry and Pericyclic Reactions. It provides discussion on
prochirality aspect, nomenclature and its applications, the concept of
stereoselectivity in classical asymmetric and stereoselective reactions, chiral
analytical chemistry for enantiomeric composition determination and peri-
cyclic reactions with more focus on frontier molecular orbital approach.
Preface xxv
A mini-review type discussion on subtopics of stereochemistry has

been intentionally excluded, as some excellent reviews are available in the
literature for researchers; otherwise this book would run into a trilogy or
more.
As some of the terms have been employed with different connotations
by various authors, the IUPAC nomenclature has been considered the
authentic form for usage in this book. Recent examples have been pro-
vided, wherever possible, with illustrative figures. Some aspects of stereo-
chemistry, that are outdated, have been discussed briefly or omitted.
Every chapter has been provided with examples to be attempted by the
students. Several excellent reviews are available on every major area of
stereochemistry; we have made use of these reviews, along with the
insight from the original papers in the present book. All the reference
materials used have been indicated as references at the end of each chap-
ter. The materials are arranged in such a way that the students can
develop a clear, concise theoretical knowledge of all aspects of stereo-
chemistry at early undergraduate and postgraduate levels.
The authors wish to acknowledge the splendid support from the
Elsevier editorial office. Some of our chemistry colleagues have helped in
bringing more clarity to the matter provided in the book. One of the
authors (AVK) wishes to thank his better half, Dr. Madhavi Karnik, an
organic chemist by training and pharmaceutical industry IP professional,
for critical discussions and valuable suggestions. Finally, the interactions
over three decades with the student community are gratefully acknowl-
edged, as it has led to clarity on the learners’ expectations and research
scholar’s cravings and culminated in the final presentation of the book.
We are hopeful that the book will contribute significantly to the
understanding of the basic and advanced concepts of stereochemistry for
the undergraduate/postgraduate students. The academic community and
researchers in the industry in chemical, biochemical, and pharmaceutical
sciences would find this as a worthy reference book on stereochemistry.
We have taken the maximum possible care to provide an error-free
material for the benefit of our readers. However, the chance of inadver-
tent mistakes cannot be dismissed. The authors would be grateful to our
chemistry colleagues if some corrections are suggested, wherever needed.
Anil V. Karnik and Mohammed Hasan

Department of Chemistry, University of Mumbai, Mumbai, Maharashtra, India
CHAPTER 1
Basic concepts of structure and

stereochemistry
1.1 Introduction
Stereochemistry is the chemistry with consideration of three dimensional
structural aspects of molecules. Thus, the study of the isomerism resulting
due to a difference in three dimensional arrangement of atoms in mole-
cules, assignment of notations for the different arrangements, methods for
determination of exact three dimensional arrangements, study of the
properties of the stereoisomers, study of their interaction with other ste-
reoisomeric species, properties related to geometrical shapes of the mole-
cule and some more similar aspects, constitute important components of
the stereochemistry. In layman’s way, many stereochemical aspects of the
molecules can be understood by linking it to behavioural patterns of peo-
ple around us. For example, most of us (B90%) are prominent right hand
users, while approximately B10% people are comfortable using their left-
hand in most tasks they perform. These left-handed people find it difficult
to use simple tools like the scissor crafted for a right-handed person. Also,
consider an example of a handshake between two people, both using their
right hands is more comfortable and strong; whereas a handshake between
the right hand of one person and the left hand of another person is rather
awkward and is therefore not as much strong. These are fascinating beha-
vioural displays of compatibility/noncompatibility of right-handed and
left-handed people, which also works similarly at molecular level, studied
as an important feature of stereochemistry. The arrangement of fingers of
the left hand and right hand are mirror images of each other, as seen in
the Fig. 1.1. The handedness, broadly known as ‘configuration,’ is abun-
dantly seen in naturally occurring compounds as exclusive selectivity. This
branch of science is especially important in biology and in the pharmaceu-
tical sciences, where this right handed and left handed nature of stereo-
chemical species and their interaction with another left handed or right
handed stereochemical species can be dissimilar. This difference in chemi-
cal behaviour is due to configurations, left-handed and right-handed
Stereochemistry © 2021 Elsevier Inc.

DOI: https://doi.org/10.1016/B978-0-12-821062-8.00011-9 All rights reserved. 3
4 Stereochemistry
Figure 1.1 Opposite sequence of fingers in the left and the right hand.
arrangements of three dimensional structures. A study of ‘configuration’ is

considered to be the major subdivision of stereochemistry.
The second aspect of stereochemistry is similar to the different postures
human body can adopt; such as standing, bending, sitting, lying down, etc.
Though, one can assume several postures, yet only a certain posture usually
is more comfortable/gainful for a particular task. Seen a sprinter at the
beginning of a race in the crouching position to get an advantageous start?
Well, it matters a lot, ask any athlete. Try to have a drink while lying
down and you automatically come to know why it is wrong. Properties of
the molecules and the ease of interaction with the other molecules is also
affected by the postures, described as the ‘conformations,’ the three dimen-
sional arrangements, possible by rotation around single sigma bonds.
Conformations can be changed rather easily, in most cases. However, pref-
erence for a particular conformation at the molecular level is a normal
occurrence. The third aspect is about the space needed by atoms/groups in
a molecule. As we know, a bulkier person finds it difficult to walk briskly
at a crowded place compared to a slim person. The bulkier person also
restricts the mobility of other people around him. This can cause irritation
and uncomfortable situations. Molecules behave similarly and therefore we
observe some slow reactions or unusual reactions when a bulky group is
encountered. It is interesting to see how molecules behave under such
strained situations. Stereochemistry actually revolves around these three fun-
damental three-dimensional aspects, the ‘configuration,’ the ‘conformation’
and the ‘bulkiness/crowding.’ The expanse of the stereochemistry, if stud-
ied systematically, is stimulating and is as much fun as interacting with the
wonderful different people around us.
Basic concepts of structure and stereochemistry 5
1.2 A brief history

The peculiar properties of three-dimensional arrangement of structures, and
importance of the same, came to the notice of the human-race quite late,
only after the year 1800, vis-a-vis the other significant scientific discoveries.
Plane polarised light was discovered by Malus in 1809. This was crucial to
study optical rotation at macroscopic and molecular level. Subsequently,
Arago and Mém (n.d.) (1811) and Biot (n.d.) (1812) have independently
observed optical activity of quartz crystal as solid macroscopic three dimen-
sional crystal properties. Later, Biot (n.d.) in 1815 extended his observation
of optical activity to organic turpentine liquid compound, displaying it as
molecular property as well in liquids. Later, in 1932 (Lowry & Snow, 1930),
Lowry (1964) demonstrated that aqueous and alcoholic solutions of sugar
and tartaric acid also display optical activity phenomenon, extending the con-
cept of chirality to individual molecules present in solutions. Though why
this happens was not interpreted then, this characteristic property became
connected to dissymmetric nature of the species, subsequently. The biggest
breakthrough came in 1848 when another French scientist Pasteur (1850),
was able to crystallise racemic mixture of sodium ammonium salt of tartaric
acid present in wine, as two hemihedral (opposite handedness) crystals of the
same molecule manually. He went on to display that the two crystals rotate
plane polarised light in solid as well as in solution, in opposite directions.
Pasteur concluded this property as connected to ‘dissymmetry’ present in
crystals as well as in molecular structures. The dissymmetric concept at
molecular level was better explained after development of organic structural
concepts such as hybridisation based three dimensional structure of carbon
atoms. Bel (1874) and Hoff (1874) have to be credited to linking the three-
dimensional arrangements to exhibit isomeric species. This brilliant contribu-
tion led to the beginning of chirality in a true sense. All these together laid
the foundation of stereochemistry and the further expanse of the same, in
coming years. Thousands of chemists have contributed to the rapid develop-
ment of modern organic stereochemistry. Knowing about the contributors
and their contribution is fascinating and it is recommended that a keen stu-
dent of the subject should read about the same to have a bird’s vision of the
development and expanse of the stereochemistry.
1.3 Molecular geometry

It is essential to learn about the parameters which define the molecular
geometry, which get correlated to the several aspects of stereochemistry.
Shapes of orbitals, simple (s and p) or hybridised (sp, sp2, sp3, etc.), come
6 Stereochemistry
under the domain of quantum mechanics, however for the present discussion
on stereochemistry, we will use various structural parameters qualitatively,
without reference to the quantum mechanics. For a thermodynamically
stable molecular geometry, few factors such as van der Waals’ radius, bond
length, bond angle, dihedral angle; play important role, besides other addi-
tional effects including resonance, hydrogen bonding etc.
1.3.1 Van der Waals’ radius

Van der Waals’ radius of an atom may be described as that one-half of the
distance between the two similar, nonbonded atoms at the possible closest
distance, where the potential energy is minimum. That is, if one brings
the two atoms further close to each other, the potential energy of the sys-
tem increases tremendously; and taking them further away also causes the
increase in potential energy to a smaller extent. If that distance between
the two nonbonded atoms is measured as 2r, than the van der Waals’
radius of that atom is considered as r. This is illustrated with the Fig. 1.2.
van der Waals’ radius, r, gives an idea about the space needed by an
atom and similarly by a group or a molecule, without any increase in
energy. Any other species, encroaching in the minimum space needed by
the atom or the molecule, causes increase in the energy. Some selected
van der Waals’ radii reported based on several X-ray diffraction data are C
(1.70), H (1.20), O (1.52), N (1.55), S (1.80), P (1.80), F (1.47), Cl
(1.75), Br (1.85), I (1.98) and Si (2.10) A°.
Figure 1.2 Variation of potential energy as a function of distance between two simi-
lar non-bonded atoms.
1.3.2 Bond length

The concept of the bond length, (l), can be visualised by considering two
atoms as balls connected by a spring (bond). The distance between the two
balls can vary by stretching or compressing the spring. Bond length of a
two bonded atoms as a diatomic molecules is the average distance between
their nuclei, which has the lowest potential energy for the molecule.
Compression or stretching of this ideal distance, referred to as bond length,
raises the potential energy of the system. The Table 1.1 shows some com-
monly encountered bond lengths of important structural units.
It must be noted that the pattern of bonding to other elements can
affect the bond lengths to some extent and the above values vary slightly
in most cases.
1.3.3 Bond angle

Bond angle [θ] is the angle between two atoms (X, Y), covalently bonded
to a third common atom (Z), as shown in Fig. 1.3.
Mixing and recasting of atomic orbitals of similar energies to give new
set of orbitals which are called as hybrid orbitals. This hybridisation concept
was proposed by Pauling (1931). These hybrid orbitals thus have different
shapes, bond angles and energies than the initial/parental interacting orbi-
tals. For example, the most common hybridisation state of carbon, sp3, is
produced by combination of one spherical 2s atomic orbital with three
Table 1.1 Some common bond lengths in organic compounds.

C X bond Bond Length (A°) Average Bond length
(hybridisation) (A°)
C H (sp3) 1.111 (ethane) 1.09
C H (sp2) 1.103 (ethylene) 1.09
C H (sp) 1.116 (dimethylacetylene) 1.09
C C (sp3) 1.533 (ethane) 1.54
C 5 C (sp2) 1.337 (ethylene) 1.31
C 5 C (sp2) 1.399 (benzene, aromatic) 1.40
CC (sp) 1.214 (dimethylacetylene) 1.20
C S (sp3) 1.807 (dimethyl sufide) 1.81
C O (sp3) 1.429 (methanol) 1.43
C 5 O (sp2) 1.210 (acetaldehyde) 1.23
C N (sp3) 1.473 (methylamine) 1.48
C 5 N (sp2) 1.344 (pyridine) 1.35
CN (sp) 1.159 (acetonitrile) 1.16
8 Stereochemistry
Figure 1.3 Bond angle between X and Y atoms connected to a common Z atom.
Figure 1.4 Bond angle and deviation observed in sp3 hybridised carbon compounds.
dumbbell shaped 2p atomic orbitals of the same carbon. The bond angle
for a sp3 hybridised carbon, in methane, is 109.5 degrees, the shape of this
tetra-substituted carbon compound is tetrahedral. The bond angle is subject
to change slightly for the same hybridisation state depending on the substi-
tution pattern. Some aspects such as steric crowding, dipolar attraction or
repulsion and conformational constraint due to cyclic geometry, are known
to cause deviation from the ideal bond angle in a given hybridised state of
an atom. For example, the bond angle between two hydrogens becomes
107 degrees at C2 of propane, due to the larger space used by two terminal
methyl groups. Three types of bond angles are found in dibromomethane:
Br C Br 5 112.9 degrees; H C Br 5 108.3 degrees; and the H C H 5
110.9 degrees. In cyclopropane, the bond angles are drastically altered with
C C C bond angle being 60 degrees only, making it highly bent and
strained bond. Fig. 1.4 shows the deviation of idealised bond angle due to
crowding and cyclic strains. Any large deviation from the ideal bond angle of
specific hybridisation causes certain strain in the molecule. The common bond
angles in different hybridization states, for carbon, oxygen and nitrogen are
shown in Table 1.2.
1.3.4 Dihedral angle

The bond angle defines the angle between the three atoms connected
to one central common atom. In comparison to that, the dihedral angle
Table 1.2 Some common hybridization states in organic chemistry with associated
bond angles and shapes.
Hybridisation state and Bond angle (degrees) Geometry
element/structural unit
sp3 (carbon) 109.5 Tetrahedral
sp2 (carbon) 120 Planar, triagonal
sp (carbon) 180 Linear
sp3 (oxygen) 104.5 Tetrahedral
sp3 (nitrogen) 107.3 Tetrahedral
Figure 1.5 Dihedral angle between C1 X and C2 Y viewed along C1 C2 bond (the
dark thick line represents the bond whereas dashed line represents the plane).
defines the angle between the groups attached to adjacent (C1 and C2)
carbon atoms. Thus, it is the angle between the plane containing C1 X
unit and the other plane containing C2 Y unit, with C1 bonded to C2
carbon atom. The dihedral angle can be better viewed with the help of
Newman’s projection formula, with C1 at the centre of the first circle and
C2 is at the back, not visible and C1 and C2 are joined to X and Y respec-
tively, as shown below in Fig. 1.5. The rotation of C1 C2 bond results in
change in position of the planes (X C1 C2 and Y C2 C1) and thus a
change in dihedral angle is observed. The change in dihedral angle gener-
ates several conformations in a molecule.
1.4 Isomers
Isomers are chemical species (ion or molecules) displaying different physical
and/or chemical properties, though having same molecular formulae and
hence the same molecular weights. When isomers have different bond con-
nectivity then they are referred to as ‘constitutional isomers’ or
10 Stereochemistry
Figure 1.6 Examples of constitutional isomeric pairs (A C).
‘structural isomers.’ For example, n-pentane and 2,2-dimethyl propane

have the same molecular formula, C5H12, but the bond connectivity is dif-
ferent in these two isomers and hence they are called as constitutional iso-
mers being simple and branched alkane. Similarly, ethylamine and N,N-
dimethylamine as well as catechol and quinol represents two separate pairs
of constitutional isomers. Constitutional isomers are different compounds
with same molecular formula, due to difference in bond connectivity, thus
clearly differing in both physical and chemical properties (Fig. 1.6).
Isomers are regarded as ‘stereoisomers’ when they have the same
molecular formula and the same bond connectivity, but they differ in the
spatial arrangements of the atoms/groups in space. The stereoisomers are fun-
damentally of two types, conformational isomers and configurational isomers.
1.4.1 Conformational isomers

Conformations or conformational isomers have different spatial arrange-
ments of atoms of a molecule but have same bond connectivity and the
same configuration, if chiral. These different arrangements are obtained by
rapid rotations around single bonds, resulting in changes of dihedral angles
between the concerned vicinal groups. The energy barriers required to
change one conformational isomer to another conformational isomer is
usually low and hence the inter conversion of conformational isomers
becomes possible at room temperature. Some conformational arrangements
are given a specific notation based on dihedral angles between the vicinal
groups, such as staggered ( 6 60 degrees), eclipsed (0 degrees) and skewed
(0 degrees , θ , 60 degrees) for ethane (Fig. 1.7A), and anti or gauche
conformation for n-butane based on relative positions of methyl group in
certain conformations as shown in Fig. 1.7B. The Fig. 1.7C gives major
conformational isomers of the enantiomer (S,S)-3-bromo-2-butanol,
obtained by rotation around the C2 C3 bond. Please note that the bond
connectivity remains the same for different conformational isomers, though
they differ in energies slightly. The 3-bromo-2-butanol is a chiral molecule
and the different conformational isomers can be obtained by rotation
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15. That appropriations by Congress for river and harbor
improvements of a national character, required for the
accommodation and security of an existing commerce, are
authorized by the constitution and justified by the obligations of
government to protect the lives and property of its citizens.
16. That a railroad to the Pacific ocean is imperatively demanded
by the interest of the whole country; that the Federal government
ought to render immediate and efficient aid in its construction; and
that as preliminary thereto, a daily overland mail should be promptly
established.
17. Finally, having thus set forth our distinctive principles and
views, we invite the co-operation of all citizens, however differing on
other questions, who substantially agree with us in their affirmance
and support.
1860.—Democratic (Douglas) Platform,
Charleston, April 23, and Baltimore, June 18.

1. Resolved, That we, the Democracy of the Union, in convention
assembled, hereby declare our affirmance of the resolutions
unanimously adopted and declared as a Platform of principles by the
Democratic convention at Cincinnati, in the year 1856, believing that
democratic principles are unchangeable in their nature when applied
to the same subject-matters; and we recommend, as the only further
resolutions, the following:
Inasmuch as differences of opinion exist in the Democratic party
as to the nature and extent of the powers of a territorial legislature,
and as to the powers and duties of Congress, under the constitution
of the United States, over the institution of slavery within the
territories:
2. Resolved, That the Democratic party will abide by the decisions
of the Supreme Court of the United States on the questions of
constitutional law.
3. Resolved, That it is the duty of the United States to afford ample
and complete protection to all its citizens, whether at home or
abroad, and whether native or foreign.
4. Resolved, That one of the necessities of the age, in a military,
commercial, and postal point of view, is speedy communication
between the Atlantic and Pacific states; and the Democratic party
pledge such constitutional government aid as will insure the
construction of a railroad to the Pacific coast at the earliest
practicable period.
5. Resolved, That the Democratic party are in favor of the
acquisition of the island of Cuba, on such terms as shall be honorable
to ourselves and just to Spain.
6. Resolved, That the enactments of state legislatures to defeat the
faithful execution of the Fugitive Slave Law are hostile in character,
subversive of the constitution, and revolutionary in their effect.
7. Resolved, That it is in accordance with the true interpretation of
the Cincinnati platform, that, during the existence of the territorial
governments, the measure of restriction, whatever it may be,
imposed by the federal constitution on the power of the territorial
legislature over the subject of domestic relations, as the same has
been, or shall hereafter be, finally determined by the Supreme Court
of the United States, shall be respected by all good citizens, and
enforced with promptness and fidelity by every branch of the general
government.
1860.—Democratic (Breckinridge) Platform.
Charleston and Baltimore.

Resolved, That the platform adopted by the Democratic party at
Cincinnati be affirmed, with following explanatory resolutions:
1. That the government of a territory, organized by an act of
Congress, is provisional and temporary; and, during its existence, all
citizens of the United States have an equal right to settle, with their
property, in the territory, without their rights, either of person or
property, being destroyed or impaired by congressional or territorial
legislation.
2. That it is the duty of the Federal government, in all its
departments, to protect, when necessary, the rights of persons and
property in the territories, and wherever else its constitutional
authority extends.
3. That when the settlers in a territory having an adequate
population form a state constitution in pursuance of law, the right of
sovereignty commences, and, being consummated by admission into
the Union, they stand on an equal footing with the people of other
states, and the state thus organized ought to be admitted into the
Federal Union, whether its constitution prohibits or recognizes the
institution of slavery.
4. That the Democratic party are in favor of the acquisition of the
island of Cuba, on such terms as shall be honorable to ourselves and
just to Spain, at the earliest practicable moment.
5. That the enactments of state legislatures to defeat the faithful
execution of the Fugitive Slave Law are hostile in character,
subversive of the constitution, and revolutionary in their effect.
6. That the Democracy of the United States recognize it as the
imperative duty of this government to protect the naturalized citizen
in all his rights, whether at home or in foreign lands, to the same
extent as its native-born citizens.
Whereas, One of the greatest necessities of the age, in a political,
commercial, postal, and military point of view, is a speedy
communication between the Pacific and Atlantic coasts; therefore, be
it
Resolved, That the Democratic party do hereby pledge themselves
to use every means in their power to secure the passage of some bill,
to the extent of the constitutional authority of Congress, for the
construction of a Pacific railroad from the Mississippi river to the
Pacific ocean, at the earliest practicable moment.
1864.—Radical Platform.
Cleveland, May 31.

1. That the Federal Union shall be preserved.
2. That the constitution and laws of the United States must be
observed and obeyed.
3. That the Rebellion must be suppressed by force of arms, and
without compromise.
4. That the rights of free speech, free press and the habeas corpus
be held inviolate, save in districts where martial law has been
proclaimed.
5. That the Rebellion has destroyed slavery; and the federal
constitution should be so amended as to prohibit its re-
establishment, and to secure to all men absolute equality before the
law.
6. That integrity and economy are demanded, at all times in the
administration of the government, and that in time of war the want
of them is criminal.
7. That the right of asylum, except for crime and subject to law, is a
recognized principle of American liberty; and that any violation of it
can not be overlooked, and must not go unrebuked.
8. That the national policy known as the “Monroe Doctrine” has
become a recognized principle; and that the establishment of an anti-
republican government on this continent by any foreign power can
not be tolerated.
9. That the gratitude and support of the nation are due to the
faithful soldiers and the earnest leaders of the Union army and navy,
for their heroic achievements and deathless valor in defense of our
imperiled country and of civil liberty.
10. That the one-term policy for the presidency, adopted by the
people, is strengthened by the force of the existing crisis, and should
be maintained by constitutional amendment.
11. That the constitution should be so amended that the President
and Vice-President shall be elected by a direct vote of the people.
12. That the question of the reconstruction of the rebellious states
belongs to the people, through their representatives in Congress, and
not to the Executive.
13. That the confiscation of the lands of the rebels, and their
distribution among the soldiers and actual settlers, is a measure of
justice.
1864.—Republican Platform.
Baltimore, June 7.
Resolved, That it is the highest duty of every American citizen to
maintain, against all their enemies, the integrity of the union and the
paramount authority of the constitution and laws of the United
States; and that, laying aside all differences of political opinions, we
pledge ourselves, as Union men, animated by a common sentiment
and aiming at a common object, to do everything in our power to aid
the government in quelling, by force of arms, the Rebellion now
raging against its authority, and in bringing to the punishment due
to their crimes the rebels and traitors arrayed against it.
Resolved, That we approve the determination of the government of
the United States not to compromise with rebels, nor to offer them
any terms of peace, except such as may be based upon an
“unconditional surrender” of their hostility and a return to their
allegiance to the constitution and laws of the United States; and that
we call upon the government to maintain this position, and to
prosecute the war with the utmost possible vigor to the complete
suppression of the Rebellion, in full reliance upon the self-sacrificing
patriotism, the heroic valor, and the undying devotion of the
American people to the country and its free institutions.
Resolved, That as slavery was the cause, and now constitutes the
strength, of this Rebellion, and as it must be always and everywhere
hostile to the principles of republican government, justice and the
national safety demand its utter and complete extirpation from the
soil of the Republic; and that we uphold and maintain the acts and
proclamations by which the government, in its own defense, has
aimed a death-blow at the gigantic evil. We are in favor, furthermore,
of such an amendment to the constitution, to be made by the people
in conformity with its provisions, as shall terminate and forever
prohibit the existence of slavery within the limits or the jurisdiction
of the United States.
Resolved, That the thanks of the American people are due to the
soldiers and sailors of the army and navy, who have periled their
lives in defense of their country and in vindication of the honor of its
flag; that the nation owes to them some permanent recognition of
their patriotism and their valor, and ample and permanent provision
for those of their survivors who have received disabling and
honorable wounds in the service of the country; and that the
memories of those who have fallen in its defense shall be held in
grateful and everlasting remembrance.
Resolved, That we approve and applaud the practical wisdom, the
unselfish patriotism, and the unswerving fidelity to the constitution
and the principles of American liberty with which Abraham Lincoln
has discharged, under circumstances of unparalleled difficulty, the
great duties and responsibilities of the presidential office; that we
approve and indorse, as demanded by the emergency and essential to
the preservation of the nation, and as within the provisions of the
constitution, the measures and acts which he has adopted to defend
the nation against its open and secret foes; that we approve,
especially, the Proclamation of Emancipation, and the employment,
as Union soldiers, of men heretofore held in slavery; and that we
have full confidence in his determination to carry these, and all other
constitutional measures essential to the salvation of the country, into
full and complete effect.
Resolved, That we deem it essential to the general welfare that
harmony should prevail in the national councils, and we regard as
worthy of public confidence and official trust those only who
cordially indorse the principles proclaimed in these resolutions, and
which should characterize the administration of the government.
Resolved, That the government owes to all men employed in its
armies, without regard to distinction of color, the full protection of
the laws of war; and that any violation of these laws, or of the usages
of civilized nations in the time of war, by the rebels now in arms,
should be made the subject of prompt and full redress.
Resolved, That foreign immigration, which in the past has added
so much to the wealth, development of resources, and increase of
power to this nation—the asylum of the oppressed of all nations—
should be fostered and encouraged by a liberal and just policy.
Resolved, That we are in favor of the speedy construction of the
railroad to the Pacific coast.
Resolved, That the national faith, pledged for the redemption of
the public debt, must be kept inviolate; and that, for this purpose, we
recommend economy and rigid responsibility in the public
expenditures and a vigorous and just system of taxation; and that it
is the duty of every loyal state to sustain the credit and promote the
use of the national currency.
Resolved, That we approve the position taken by the government,
that the people of the United States can never regard with
indifference the attempt of any European power to overthrow by
force, or to supplant by fraud, the institutions of any republican
government on the western continent, and that they will view with
extreme jealousy, as menacing to the peace and independence of
this, our country, the efforts of any such power to obtain new
footholds for monarchical governments, sustained by a foreign
military force, in near proximity to the United States.
1864.—Democratic Platform.
Chicago, August 29.

Resolved, That in the future, as in the past, we will adhere with
unswerving fidelity to the Union under the constitution, as the only
solid foundation of our strength, security, and happiness as a people,
and as a framework of government equally conducive to the welfare
and prosperity of all the states, both northern and southern.
Resolved, That this convention does explicitly declare, as the sense
of the American people, that after four years of failure to restore the
Union by the experiment of war, during which, under the pretense of
a military necessity of a war power higher than the constitution, the
constitution itself has been disregarded in every part, and public
liberty and private right alike trodden down, and the material
prosperity of the country essentially impaired, justice, humanity,
liberty, and the public welfare demand that immediate efforts be
made for a cessation of hostilities, with a view to an ultimate
convention of all the states, or other peaceable means, to the end
that, at the earliest practicable moment, peace may be restored on
the basis of the federal union of all the states.
Resolved, That the direct interference of the military authority of
the United States in the recent elections held in Kentucky, Maryland,
Missouri, and Delaware, was a shameful violation of the constitution;
and the repetition of such acts in the approaching election will be
held as revolutionary, and resisted with all the means and power
under our control.
Resolved, That the aim and object of the Democratic party is to
preserve the Federal Union and the rights of the states unimpaired;
and they hereby declare that they consider the administrative
usurpation of extraordinary and dangerous powers not granted by
the constitution, the subversion of the civil by the military law in
states not in insurrection, the arbitrary military arrest,
imprisonment, trial, and sentence of American citizens in states
where civil law exists in full force, the suppression of freedom of
speech and of the press, the denial of the right of asylum, the open
and avowed disregard of state rights, the employment of unusual test
oaths, and the interference with and denial of the right of the people
to bear arms in their defense, as calculated to prevent a restoration of
the Union and the perpetuation of a government deriving its just
powers from the consent of the governed.
Resolved, That the shameful disregard of the administration to its
duty in respect to our fellow-citizens who now are, and long have
been, prisoners of war, in a suffering condition, deserves the severest
reprobation, on the score alike of public policy and common
humanity.
Resolved, That the sympathy of the Democratic party is heartily
and earnestly extended to the soldiery of our army and the sailors of
our navy, who are and have been in the field and on the sea under the
flag of their country; and, in the event of our attaining power, they
will receive all the care and protection, regard and kindness, that the
brave soldiers of the Republic have so nobly earned.
1868. Republican Platform.
Chicago, May 20.

1. We congratulate the country on the assured success of the
reconstruction policy of Congress, as evinced by the adoption, in the
majority of the states lately in rebellion, of constitutions securing
equal civil and political rights to all; and it is the duty of the
government to sustain those institutions and to prevent the people of
such states from being remitted to a state of anarchy.
2. The guarantee by Congress of equal suffrage to all loyal men at
the south was demanded by every consideration of public safety, of
gratitude, and of justice, and must be maintained; while the question
of suffrage in all the loyal states properly belongs to the people of
those states.
3. We denounce all forms of repudiation as a national crime; and
the national honor requires the payment of the public indebtedness
in the uttermost good faith to all creditors at home and abroad, not
only according to the letter but the spirit of the laws under which it
was contracted.
4. It is due to the labor of the nation that taxation should be
equalized and reduced as rapidly as the national faith will permit.
5. The national debt, contracted as it has been for the preservation
of the Union for all time to come, should be extended over a fair
period for redemption; and it is the duty of Congress to reduce the
rate of interest thereon whenever it can be honestly done.
6. That the best policy to diminish our burden of debts is to so
improve our credit that capitalists will seek to loan us money at lower
rates of interest than we now pay, and must continue to pay, so long
as repudiation, partial or total, open or covert, is threatened or
suspected.
7. The government of the United States should be administered
with the strictest economy; and the corruptions which have been so
shamefully nursed and fostered by Andrew Johnson call loudly for
radical reform.
8. We profoundly deplore the tragic death of Abraham Lincoln,
and regret the accession to the presidency of Andrew Johnson, who
has acted treacherously to the people who elected him and the cause
he was pledged to support; who has usurped high legislative and
judicial functions; who has refused to execute the laws; who has used
his high office to induce other officers to ignore and violate the laws;
who has employed his executive powers to render insecure the
property, the peace, liberty, and life of the citizen; who has abused
the pardoning power; who has denounced the national legislature as
unconstitutional; who has persistently and corruptly resisted, by
every means in his power, every proper attempt at the reconstruction
of the states lately in rebellion; who has perverted the public
patronage into an engine of wholesale corruption; and who has been
justly impeached for high crimes and misdemeanors, and properly
pronounced guilty thereof by the vote of thirty-five Senators.
9. The doctrine of Great Britain and other European powers, that
because a man is once a subject he is always so, must be resisted at
every hazard by the United States, as a relic of feudal times, not
authorized by the laws of nations, and at war with our national honor
and independence. Naturalized citizens are entitled to protection in
all their rights of citizenship as though they were native-born; and no
citizen of the United States, native or naturalized, must be liable to
arrest and imprisonment by any foreign power for acts done or
words spoken in this country; and, if so arrested and imprisoned, it is
the duty of the government to interfere in his behalf.
10. Of all who were faithful in the trials of the late war, there were
none entitled to more special honor than the brave soldiers and
seamen who endured the hardships of campaign and cruise, and
imperiled their lives in the service of the country. The bounties and
pensions provided by the laws for these brave defenders of the nation
are obligations never to be forgotten; the widows and orphans of the
gallant dead are the wards of the people—a sacred legacy bequeathed
to the nation’s protecting care.
11. Foreign immigration, which in the past has added so much to
the wealth, development, and resources, and increase of power to
this Republic, the asylum of the oppressed of all nations, should be
fostered and encouraged by a liberal and just policy.
12. This convention declares itself in sympathy with all oppressed
people who are struggling for their rights.
13. That we highly commend the spirit of magnanimity and
forbearance with which men who have served in the Rebellion, but
who now frankly and honestly co-operate with us in restoring the
peace of the country and reconstructing the southern state
governments upon the basis of impartial justice and equal rights, are
received back into the communion of the loyal people; and we favor
the removal of the disqualifications and restrictions imposed upon
the late rebels, in the same measure as the spirit of disloyalty shall
die out, and as may be consistent with the safety of the loyal people.
14. That we recognize the great principles laid down in the
immortal Declaration of Independence, as the true foundation of
democratic government; and we hail with gladness every effort
toward making these principles a living reality on every inch of
American soil.
1868.—Democratic Platform.
New York, July 4.

The Democratic party, in national convention assembled, reposing
its trust in the intelligence, patriotism, and discriminating justice of
the people, standing upon the constitution as the foundation and
limitation of the powers of the government and the guarantee of the
liberties of the citizen, and recognizing the questions of slavery and
secession as having been settled, for all time to come, by the war or
voluntary action of the southern states in constitutional conventions
assembled, and never to be revived or re-agitated, do, with the return
of peace, demand—
1. Immediate restoration of all the states to their rights in the
Union under the constitution, and of civil government to the
American people.
2. Amnesty for all past political offenses, and the regulation of the
elective franchise in the states by their citizens.
3. Payment of all the public debt of the United States as rapidly as
practicable—all money drawn from the people by taxation, except so
much as is requisite for the necessities of the government,
economically administered, being honestly applied to such payment;
and where the obligations of the government do not expressly state
upon their face, or the law under which they were issued does not
provide that they shall be paid in coin, they ought, in right and in
justice, to be paid in the lawful money of the United States.
4. Equal taxation of every species of property according to its real
value, including government bonds and other public securities.
5. One currency for the government and the people, the laborer
and the office-holder, the pensioner and the soldier, the producer
and the bondholder.
6. Economy in the administration of the government; the
reduction of the standing army and navy; the abolition of the
Freedmen’s Bureau and all political instrumentalities designed to
secure negro supremacy; simplification of the system and
discontinuance of inquisitorial modes of assessing and collecting
internal revenue; that the burden of taxation may be equalized and
lessened, and the credit of the government and the currency made
good; the repeal of all enactments for enrolling the state militia into
national forces in time of peace; and a tariff for revenue upon foreign
imports, and such equal taxation under the internal revenue laws as
will afford incidental protection to domestic manufactures, and as
will, without impairing the revenue, impose the least burden upon,
and best promote and encourage, the great industrial interests of the
country.
7. Reform of abuses in the administration; the expulsion of corrupt
men from office; the abrogation of useless offices; the restoration of
rightful authority to, and the independence of, the executive and
judicial departments of the government; the subordination of the
military to the civil power, to the end that the usurpations of
Congress and the despotism of the sword may cease.
8. Equal rights and protection for naturalized and native-born
citizens, at home and abroad; the assertion of American nationality
which shall command the respect of foreign powers, and furnish an
example and encouragement to people struggling for national
integrity, constitutional liberty and individual rights; and the
maintenance of the rights of naturalized citizens against the absolute
doctrine of immutable allegiance and the claims of foreign powers to
punish them for alleged crimes committed beyond their jurisdiction.
In demanding these measures and reforms, we arraign the Radical
party for its disregard of right and the unparalleled oppression and
tyranny which have marked its career. After the most solemn and
unanimous pledge of both Houses of Congress to prosecute the war
exclusively for the maintenance of the government and the
preservation of the Union under the constitution, it has repeatedly
violated the most sacred pledge under which alone was rallied that
noble volunteer army which carried our flag to victory. Instead of
restoring the Union, it has, so far as in its power, dissolved it, and
subjected ten states, in time of profound peace, to military despotism
and negro supremacy. It has nullified there the right of trial by jury;
it has abolished the habeas corpus, that most sacred writ of liberty; it
has overthrown the freedom of speech and press; it has substituted
arbitrary seizures and arrests, and military trials and secret star-
chamber inquisitions, for the constitutional tribunals; it has
disregarded, in time of peace, the right of the people to be free from
searches and seizures; it has entered the post and telegraph offices,
and even the private rooms of individuals, and seized their private
papers and letters, without any specific charge or notice of affidavit,
as required by the organic law. It has converted the American capitol
into a bastile; it has established a system of spies and official
espionage to which no constitutional monarchy of Europe would now
dare to resort. It has abolished the right of appeal, on important
constitutional questions, to the supreme judicial tribunals, and
threatens to curtail or destroy its original jurisdiction, which is
irrevocably vested by the constitution; while the learned Chief
Justice has been subjected to the most atrocious calumnies, merely
because he would not prostitute his high office to the support of the
false and partisan charges preferred against the President. Its
corruption and extravagance have exceeded anything known in
history; and, by its frauds and monopolies, it has nearly doubled the
burden of the debt created by the war. It has stripped the President
of his constitutional power of appointment, even of his own cabinet.
Under its repeated assaults, the pillars of the government are rocking
on their base; and should it succeed in November next, and
inaugurate its President, we will meet, as a subjected and conquered
people, amid the ruins of liberty and the scattered fragments of the
constitution.
And we do declare and resolve that ever since the people of the
United States threw off all subjection to the British crown, the
privilege and trust of suffrage have belonged to the several states,
and have been granted, regulated, and controlled exclusively by the
political power of each state respectively; and that any attempt by
Congress, on any pretext whatever, to deprive any state of this right,
or interfere with its exercise, is a flagrant usurpation of power which
can find no warrant in the constitution, and, if sanctioned by the
people, will subvert our form of government, and can only end in a
single, centralized, and consolidated, government, in which the
separate existence of the states will be entirely absorbed, and an
unqualified despotism be established in place of a federal union of
co-equal states. And that we regard the construction acts (so called)
of Congress as usurpations, and unconstitutional, revolutionary, and
void.
That our soldiers and sailors, who carried the flag of our country to
victory against the most gallant and determined foe, must ever be
gratefully remembered, and all the guarantees given in their favor
must be faithfully carried into execution.
That the public lands should be distributed as widely as possible
among the people, and should be disposed of either under the pre-
emption of homestead lands or sold in reasonable quantities, and to
none but actual occupants, at the minimum price established by the
government. When grants of public lands may be allowed, necessary
for the encouragement of important public improvements, the
proceeds of the sale of such lands, and not the lands themselves,
should be so applied.
That the President of the United States, Andrew Johnson, in
exercising the power of his high office in resisting the aggressions of
Congress upon the constitutional rights of the states and the people,
is entitled to the gratitude of the whole American people; and, on
behalf of the Democratic party, we tender him our thanks for his
patriotic efforts in that regard.
Upon this platform, the Democratic party appeal to every patriot,
including all the conservative element and all who desire to support
the constitution and restore the Union, forgetting all past differences
of opinion, to unite with us in the present great struggle for the
liberties of the people; and that to all such, to whatever party they
may have heretofore belonged, we extend the right hand of
fellowship, and hail all such, co-operating with us, as friends and
brethren.
Resolved, That this convention sympathizes cordially with the
workingmen of the United States in their efforts to protect the rights
and interests of the laboring classes of the country.
Resolved, That the thanks of the convention are tendered to Chief
Justice Salmon P. Chase, for the justice, dignity, and impartiality
with which he presided over the court of impeachment on the trial of
President Andrew Johnson.
1872.—Labor Reform Platform.
Columbus, February 21.

We hold that all political power is inherent in the people, and free
government founded on their authority and established for their
benefit; that all citizens are equal in political rights, entitled to the
largest religious and political liberty compatible with the good order
of society, as also the use and enjoyment of the fruits of their labor
and talents; and no man or set of men is entitled to exclusive
separable endowments and privileges or immunities from the
government, but in consideration of public services; and any laws
destructive of these fundamental principles are without moral
binding force, and should be repealed. And believing that all the evils
resulting from unjust legislation now affecting the industrial classes
can be removed by the adoption of the principles contained in the
following declaration: therefore,
Resolved, That it is the duty of the government to establish a just
standard of distribution of capital and labor, by providing a purely
national circulating medium, based on the faith and resources of the
nation, issued directly to the people without the intervention of any
system of banking corporations, which money shall be legal tender in
the payment of all debts, public and private, and interchangeable, at
the option of the holder, for government bonds bearing a rate of
interest not to exceed 3.65 per cent., subject to future legislation by
Congress.
2. That the national debt should be paid in good faith, according to
the original contract, at the earliest option of the government,
without mortgaging the property of the people or the future
exigencies of labor to enrich a few capitalists at home and abroad.
3. That justice demands that the burdens of government should be
so adjusted as to bear equally on all classes, and that the exemption
from taxation of government bonds bearing extravagant rates of
interest, is a violation of all just principles of revenue laws.
4. That the public lands of the United States belong to the people,
and should not be sold to individuals nor granted to corporations,
but should be held as a sacred trust for the benefit of the people, and
should be granted to landless settlers only, in amounts not exceeding
one hundred and sixty acres of land.
5. That Congress should modify the tariff so as to admit free such
articles of common use as we can neither produce nor grow, and lay
duties for revenue mainly upon articles of luxury and upon such
articles of manufacture as will, we having the raw materials, assist in
further developing the resources of the country.
6. That the presence in our country of Chinese laborers, imported
by capitalists in large numbers for servile use is an evil entailing want
and its attendant train of misery and crime on all classes of the
American people, and should be prohibited by legislation.
7. That we ask for the enactment of a law by which all mechanics
and day-laborers employed by or on behalf of the government,
whether directly or indirectly, through persons, firms, or
corporations, contracting with the state, shall conform to the reduced
standard of eight hours a day, recently adopted by Congress for
national employes; and also for an amendment to the acts of
incorporation for cities and towns, by which all laborers and
mechanics employed at their expense shall conform to the same
number of hours.
8. That the enlightened spirit of the age demands the abolition of
the system of contract labor in our prisons and other reformatory
institutions.
9. That the protection of life, liberty, and property are the three
cardinal principles of government, and the first two are more sacred
than the latter; therefore, money needed for prosecuting wars
should, as it is required, be assessed and collected from the wealthy
of the country, and not entailed as a burden on posterity.
10. That it is the duty of the government to exercise its power over
railroads and telegraph corporations, that they shall not in any case
be privileged to exact such rates of freight, transportation, or
charges, by whatever name, as may bear unduly or unequally upon
the producer or consumer.
11. That there should be such a reform in the civil service of the
national government as will remove it beyond all partisan influence,
and place it in the charge and under the direction of intelligent and
competent business men.
12. That as both history and experience teach us that power ever
seeks to perpetuate itself by every and all means, and that its
prolonged possession in the hands of one person is always dangerous
to the interests of a free people, and believing that the spirit of our
organic laws and the stability and safety of our free institutions are
best obeyed on the one hand, and secured on the other, by a regular
constitutional change in the chief of the country at each election;
therefore, we are in favor of limiting the occupancy of the
presidential chair to one term.
13. That we are in favor of granting general amnesty and restoring
the Union at once on the basis of equality of rights and privileges to
all, the impartial administration of justice being the only true bond of
union to bind the states together and restore the government of the
people.
14. That we demand the subjection of the military to the civil
authorities, and the confinement of its operations to national
purposes alone.
15. That we deem it expedient for Congress to supervise the patent
laws so as to give labor more fully the benefit of its own ideas and
inventions.
16. That fitness, and not political or personal considerations,
should be the only recommendation to public office, either
appointive or elective; and any and all laws looking to the
establishment of this principle are heartily approved.
1872.—Prohibition Platform.
Columbus, Ohio, February 22.

The preamble recites that protection and allegiance are reciprocal
duties; and every citizen who yields obediently to the full commands
of government should be protected in all enjoyment of personal
security, personal liberty, and private property. That the traffic in
intoxicating drinks greatly impairs the personal security and
personal liberty of a great mass of citizens, and renders private
property insecure. That all political parties are hopelessly unwilling
to adopt an adequate policy on this question: Therefore, as a national
convention, we adopt the following declaration of principles:
That while we acknowledge the pure patriotism and profound
statesmanship of those patriots who laid the foundation of this
government, securing at once the rights of the states severally and
their inseparable union by the federal constitution, we would not
merely garnish the sepulchres of our republican fathers, but we do
hereby renew our pledges of solemn fealty to the imperishable
principles of civil and religious liberty embodied in the Declaration
of Independence and our federal constitution.
That the traffic in intoxicating beverages is a dishonor to Christian
civilization, a political wrong of unequalled enormity, subversive of
ordinary objects of government, not capable of being regulated or
restrained by any system of license whatever, and imperatively
demands, for its suppression, effective legal prohibition, both by
state and national legislation.
That there can be no greater peril to a nation than existing party
competition for the liquor vote. That any party not opposed to the
traffic, experience shows will engage in this competition—will court
the favor of criminal classes—will barter away the public morals, the
purity of the ballot, and every object of good government, for party
success.
That, as prohibitionists, we will individually use all efforts to
persuade men from the use of intoxicating liquors; and we invite all
persons to assist in this movement.
That competence, honesty, and sobriety are indispensable
qualifications for holding office.
That removals from public office for mere political differences of
opinion are wrong.
That fixed and moderate salaries of public officers should take the
places of fees and perquisites; and that all means should be taken to
prevent corruption and encourage economy.
That the President and Vice-President should be elected directly
by the people.
That we are in favor of a sound national currency, adequate to the
demands of business, and convertible into gold and silver at the will
of the holder, and the adoption of every measure compatible with
justice and public safety to appreciate our present currency to the
gold standard.
That the rates of ocean and inland postage, and railroad telegraph
lines and water transportation, should be made as low as possible by
law.
That we are opposed to all discrimination in favor of capital
against labor, as well as all monopoly and class legislation.
That the removal of the burdens imposed in the traffic in
intoxicating drinks will emancipate labor, and will practically
promote labor reform.
That suffrage should be granted to all persons, without regard to
sex.
That the fostering and extension of common schools is a primary
duty of the government.
That a liberal policy should be pursued to promote foreign
immigration.
1872.—Liberal Republican Platform.
Cincinnati, May 1.
We, the Liberal Republicans of the United States, in national
convention assembled at Cincinnati, proclaim the following
principles as essential to just government.
1. We recognize the equality of all men before the law, and hold
that it is the duty of government, in its dealings with the people, to
mete out equal and exact justice to all, of whatever nativity, race,
color, or persuasion, religious or political.
2. We pledge ourselves to maintain the union of these states,
emancipation, and enfranchisement, and to oppose any reopening of
the questions settled by the thirteenth, fourteenth, and fifteenth
amendments of the constitution.
3. We demand the immediate and absolute removal of all
disabilities imposed on account of the Rebellion, which was finally
subdued seven years ago, believing that universal amnesty will result
in complete pacification in all sections of the country.
4. Local self-government, with impartial suffrage, will guard the
rights of all citizens more securely than any centralized power. The
public welfare requires the supremacy of the civil over the military
authority, and the freedom of person under the protection of the
habeas corpus. We demand for the individual the largest liberty
consistent with public order, for the state self-government, and for
the nation a return to the methods of peace and the constitutional
limitations of power.
5. The civil service of the government has become a mere
instrument of partisan tyranny and personal ambition, and an object
of selfish greed. It is a scandal and reproach upon free institutions,
and breeds a demoralization dangerous to the perpetuity of
republican government. We, therefore, regard a thorough reform of
the civil service as one of the most pressing necessities of the hour;
that honesty, capacity, and fidelity constitute the only valid claims to
public employment; that the offices of the government cease to be a
matter of arbitrary favoritism and patronage, and that public station
shall become again a post of honor. To this end, it is imperatively
required that no President shall be a candidate for re-election.
6. We demand a system of federal taxation which shall not
unnecessarily interfere with the industry of the people, and which
shall provide the means necessary to pay the expenses of the
government, economically administered, the pensions, the interest
on the public debt, and a moderate reduction annually of the
principal thereof; and recognizing that there are in our midst honest
but irreconcilable differences of opinion with regard to the respective
systems of protection and free trade, we remit the discussion of the
subject to the people in their congressional districts and the decision
of Congress thereon, wholly free from Executive interference or
dictation.
7. The public credit must be sacredly maintained, and we
denounce repudiation in every form and guise.
8. A speedy return to specie payment is demanded alike by the
highest considerations of commercial morality and honest
government.
9. We remember with gratitude the heroism and sacrifices of the
soldiers and sailors of the Republic; and no act of ours shall ever

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Stereochemistry: A Three-Dimensional

Insight Anil V. Karnik And Mohammed

Pericyclic chemistry. Orbital mechanisms and

Abnormal Psychology and Life: A Dimensional Approach

Data analytics Anil Maheshwari

eTextbook 978-1337098106 Abnormal Psychology and Life:

Lifeworlds of Islam: The Pragmatics of a Religion

Big Data Anil Maheshwari

Abnormal Psychology and Life: A Dimensional Approach

Memupuk Kesabaran Saat Belajar Yuni Hasan

For Information on all Elsevier publications

Publisher: Susan Dennis

About the authors xvii

Part I Fundamentals of stereochemistry

2. Symmetry and point groups 25

2.3 Point groups and their classification 33

3. Elements of chirality and chiral stereoisomerism 49

3.5.4 Chiral ferrocenes 81

Part II Enantiomer properties

5. Configurational analysis 129

6. Racemates: Properties and methods of resolution 187

Part III Conformations and conformational analysis

7.2.1 Torsional strain 228

8. Conformations of cyclic, fused and bridged ring molecules 273

8.7 Cyclobutane conformations 300

8.19.7 Tricyclo[1.1.1.0]pentane or [1.1.1]propellane 345

Part IV Stereochemical reactivity

10. Diastereomeric transition states and stereoselectivity 407

11. Chiral analytical chemistry 465

11.3 Chiroptical methods for determination of enantiomer composition 469

12. Pericyclic reactions 515

12.4.1 Application of FMO approach to cyclo-addition reactions 530

Solutions and keys to the problems 551

Prof. Anil V. Karnik worked as a Professor of Organic Chemistry and

Dr. Mohammed Hasan graduated with a PhD in Organic Chemistry

Stereochemistry is the most stimulating and important topic for any

chemists equally. It is a much-welcomed addition to the repertoire of

This book has been written for the undergraduate/postgraduate and

different species. More clarity has emerged in understanding the reactivity

A mini-review type discussion on subtopics of stereochemistry has

Anil V. Karnik and Mohammed Hasan

Basic concepts of structure and

Stereochemistry © 2021 Elsevier Inc.

arrangements of three dimensional structures. A study of ‘configuration’ is

1.2 A brief history

1.3 Molecular geometry

1.3.1 Van der Waals’ radius

1.3.2 Bond length

1.3.3 Bond angle

Table 1.1 Some common bond lengths in organic compounds.

1.3.4 Dihedral angle

Figure 1.6 Examples of constitutional isomeric pairs (A C).

‘structural isomers.’ For example, n-pentane and 2,2-dimethyl propane

1.4.1 Conformational isomers

1860.—Democratic (Douglas) Platform,

Charleston, April 23, and Baltimore, June 18.

1860.—Democratic (Breckinridge) Platform.

Charleston and Baltimore.

Cleveland, May 31.