Organic Conformational Analysis and Stereochemistry from Circular Dichroism Spectroscopy

by Lightner, David A.; Gurst, Jerome E.

• ISBN13: 9780471354055
• ISBN10: 0471354058
• Edition: 1st
• Format: Hardcover
• Copyright: 2000-03-31
• Publisher: Wiley-VCH

Summary

* An interesting historical account of the development of stereochemical concepts

Author Biography

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

Table of Contents

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