Organic Conformational Analysis and

* An interesting historical account of the development of stereochemical concepts

DAVID A. LIGHTNER, PhD, is R. C. Fuson Professor of Chemistry at the University of Nevada, Reno. JEROME E. GURST, PhD, is Professor of Chemistry at the University of West Florida, Pensacola.

Preface

xi

Introduction

1

(4)

References

4

(1)

Cyclohexane and Cyclohexanone

5

(32)

Cyclohexane

5

(8)

Cyclohexane and Dynamic NMR

13

(3)

Substituted Cyclohexanes and Dynamic NMR

16

(6)

Conformation from Molecular Mechanics

22

(2)

Cyclohexanone

24

(3)

Substituted Cyclohexanones

27

(4)

Substituted Cyclohexanones, Optical Activity, and Circular Dichroism

31

(6)

References

33

(4)

Optical Activity

37

(26)

Absorption of Light and Its Relationship to Optical Activity

37

(3)

The Origin of Optical Activity

40

(5)

Angle of Rotation (&phis;, α) and Optical Rotary Dispersion (ORD)

45

(2)

Angle of Ellipticity (&thetas;) and Circular Dichroism (Δε)

47

(3)

Quantitative Relationship Between CD and ORD

50

(1)

The Magnitude of Optical Activity, Cotton Effects, and Rotatory Strength

51

(1)

Optical Activity of Chromophores

52

(1)

Limiting Classification of Chromophores as Inherently Symmetric or Inherently Dissymmetric

53

(10)

References

56

(1)

Appendix: Experimental Rotatory Strengths

56

(7)

The Octant Rule

63

(32)

Optical Activity of the Ketone n → π* Electronic Transition

64

(1)

Formulation of the Octant Rule from Carbonyl n → π* Nodal Planes

65

(1)

How to Use the Octant Rule to Determine Absolute Stereochemistry and Conformation

66

(5)

The Question of Front Octants

71

(3)

The Location and Shape of the Third Nodal Surface: ``Anti-Octant'' Effects

74

(5)

Perturbers Lying in Octant Symmetry Planes: Qualitative Completeness and the Octant Rule

79

(2)

Octant Rule Theory and Analysis

81

(4)

The Octant Rule and Octant Surfaces

85

(1)

Mechanism of Optical Activity and CD from Octant Consignate and Dissignate W-Coupling Paths

86

(1)

Ketone Carbonyl Short-Wavelength Transitions

87

(8)

References

92

(3)

Conformational Analysis of Substituted Cyclohexanones

95

(44)

2-Methylcyclohexanone and 2-Methy 1-4-tert-butycyclohexanone

95

(5)

Other Conformationally Immobilized α-Methylcyclohexanones

100

(5)

2-Isopropyl and 2-tert-Butylcyclohexanone

105

(4)

3-Methylcyclohexanone

109

(2)

trans-2-Bromo- and 2-Chloro-5-methylcyclohexanone

111

(5)

Conformer Populations and ΔG from Variable-Temperature CD

116

(2)

Dimethyl- and Trimethylcyclohexanones

118

(6)

Bisignate n → π* Cotton Effects: Menthone and Isomenthone

124

(10)

Intramolecular Hydrogen Bonding and 2-Oxo-1-p-menthanol

134

(5)

References

136

(3)

Other Cycloalkanones

139

(46)

Cyclopropane and Cyclopropanone

139

(1)

Cyclobutane and Cyclobutanones

140

(8)

Cyclopentane

148

(6)

Cyclopentanones

154

(19)

Cycloheptane, Cycloheptanones and Larger Rings

173

(12)

References

182

(3)

Saturated Bicyclic Ketones

185

(46)

Decalins (Bicyclo[4.4.0]decanes)

185

(4)

Decalones

189

(18)

Hydrindanes (Bicyclo[4.3.0]nonanes)

207

(5)

Hydrindanones

212

(5)

Other Bicyclo[m.n.0]alkanones

217

(2)

Spiro[m.n]alkanones

219

(2)

Bridged Bicyclo[m.n.o]alkanones

221

(10)

References

227

(4)

Saturated Polycylic Ketones

231

(44)

Tricyclic Ketones: Perhydrophenanthrenones and Perhydroanthracenones

234

(1)

Tetracyclic Ketones: Steroids

235

(4)

Conformational Distortions in Steroid and Triterpene Ketones

239

(14)

Variable-Temperature CD Studies of Steroid and Triterpene Ketones

253

(9)

Influence of Solvent on the Cotton Effects of Steroid Ketones

262

(3)

Bridged-ring Polycyclic Ketones

265

(10)

References

271

(4)

Isotopically Perturbed Ketones

275

(30)

Deuterated Cyclopentanones

276

(5)

Deuterated Cyclohexanones

281

(10)

Deuterated Cyclobutanones

291

(2)

Trideuteriomethyl Perturbers

293

(2)

13C as an Octant Perturber

295

(2)

Isotopic Perturbation of Diketones

297

(1)

Isotopically Perturbed β,γ-Unsaturated Ketones

298

(1)

Isotopic Perturbers and the Octant Rule

299

(2)

Other Isotopically Perturbed Chromophores

301

(4)

References

301

(4)

Diketones

305

(32)

Additivity of Octant Contributions vs. Vicinal Interaction

306

(5)

Transannular Orbital Interaction in Nonconjugated Diketones

311

(6)

Remote Diketones: γ-and δ-Diones

317

(4)

Proximal Diketones: β-Diones

321

(8)

Adjacent Diketones: α-Diones

329

(8)

References

332

(5)

Unsaturated and Cyclopropyl Ketones

337

(58)

α, β-Unsaturated Ketones

339

(13)

β,γ-Unsaturated Ketones and the Extended Octant Rule

352

(19)

γ,δ-and δ,ε-Unsaturated Ketones and Beyond

371

(10)

Cyclopropyl Ketones

381

(14)

References

390

(5)

Dienes

395

(14)

Olefin Sector Rules

395

(4)

Alkenes: The Current Situation

399

(1)

Conjugated Dienes

400

(9)

References

407

(2)

Biaryls and Helicenes

409

(14)

Benzene Sector Rules

409

(6)

Biaryls as Dissymmetric Chromophores

415

(3)

Helicenes

418

(5)

References

420

(3)

Exciton Coupling and Exciton Chirality

423

(34)

Origin of Exciton Coupling

423

(3)

Orientation Dependence in Exciton Coupling

426

(2)

Exciton Coupling and Circular Dichroism

428

(2)

The Exciton Chirality Rule

430

(1)

Absolute Configuration from Excition Chirality

431

(8)

Additivity of Pairwise Exciton Couplings in Polychromophore Systems

439

(1)

Red-shifted Chromophores

440

(1)

Bisignate CD Sign Inversions

440

(4)

Enhanced Sensitivity by Fluorescence-Detected CD

444

(1)

Applications of the Exciton Chirality Rule

445

(12)

References

454

(3)

Index to Chiroptical Data and Spectra

457

(14)

Subject Index

471

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Organic Conformational Analysis and Stereochemistry from Circular Dichroism Spectroscopy

Summary

Author Biography

Table of Contents

Supplemental Materials