Alicyclic Compounds

Preface

List of Common Abbreviations and Symbols Used

Chapter 1. Alicyclic Hydrocarbons, Conformation and Stereochemistry


1. Introduction


2. Three-Membered Rings

(a) Cyclopropanes with Unsaturated Substituents

(b) Cyclopropanes with Saturated Substituents


3. Four-Membered Rings

(a) Cyclobutanes

(b) Monosubstituted Cyclobutanes

(c) Disubstituted Cyclobutanes

(d) Unsaturated Four-Membered Ring Carbocycles

(e) Cyclobutanones


4. Five-Membered Rings

(a) Cyclopentane

(b) Cyclopentene

(c) Cyclopentanone


5. Six-Membered Rings

(a) Cyclohexane

(b) Monosubstituted Cyclohexanes

(c) 1,1-Disubstituted Cyclohexanes

(d) 1,2-Disubstituted Cyclohexanes

(e) 1,1,2-Trisubstituted Cyclohexanes

(f) 1,3- and 1,3,5-Substituted Cyclohexanes

(g) 1,4-Disubstituted Cyclohexanes

(h) Sterically Crowded Cyclohexanes

(i) Cyclohexene

(j) 1,3-Cyclohexadiene

(k) 1,4-Cyclohexadienes

(l) Exomethylenecyclohexane

(m)Cyclohexanones, Cyclohexanediones and Cyclohexenones


6. Seven-Membered Rings

(a) Cycloheptanes

(b) Cycloheptanones

(c) Cycloheptene and Cycloheptene Oxide

(d) Cyeloheptadienes and Cycloheptatrienes


7. Eight-Membered Rings

(a) Cyclooctanes

(b) Cyclooctanones

(c) Cyclooctene, Cyclooctyne and 1,2-Cyclooctadiene

(d) 1,3-, 1,4- and 1,5-Cyclooctadienes

(e) Cyclooctatrienes


8. Nine-Membered Rings

(a) Cyclononane, Cyclononanone and Cyclononyne

(b) 1,2-Cyclononadiene and 1,5-Cyclononadiene

(c) Cyclononatrienes


9. Ten-Membered Rings


10. Ring Systems Larger than Ten-Membered

Chapter 2. The Cyclopropanes


1. Introduction


2. Preparation of Cyclopropanes

(a) Intramolecular Nucleophilic Substitution

(b) Simmons-Smith Reaction

(c) Reaction of Alkenes with Diazo Compounds

(d) Reaction of Alkenes with Dihalocarbenes and Other Carbenoids

(e) Ring Contraction of Cyclobutanes

(F) Reactions of Electron Deficient Carbon-Carbon Double Bonds with Phosphoranes, Sulfuranes and Arsenic Ylides

(G) Photochemical Reaction

(H) Radical Mediated Reaction

(I) Organometallic Reaction

(J) Miscellaneous Reaction


3. Use of Cyclopropanes in Organic Synthesis

(a) Thermal Ring Fission

(b) Reductive and Oxidative Ring Fission

(c) Electrophilic and Nucleophilic Ring Fission

(d) Radical Mediated Ring Fission

(e) Metal Salt Mediated Ring Fission

Chapter 3. The Cyclobutanes


1. Introduction, Structure, Properties, and Theoretical Considerations


2. Synthesis of the Cyclobutane Ring System

(a) [2+2] Cycloaddition Reactions

(b) Intramolecular Cyclisations

(c) Ring Expansion Reactions

(d) Ring Contractions


3. Reactions of Cyclobutanes

(a) Solvolyses and Rearrangements of Cyclobutanes and Cyclobutenes

(b) Electrocyclic Ring Opening-Ring Closing Reactions

(c) Miscellaneous Reactions of Cyclobutanes and Cyclobutenes

(d) Reactions of Cyclobutanols, Cyclobutanones and Cyclobutenones

(e) Reactions of Cyclobutenenitriles

(F) Reactions of Squaric and Semisquaric Acids

Chapter 4a. The Cyclopentanes


1. Reviews, Theoretical and Structural Aspects, General Properties


2. Synthesis

(a) Cyclisation Reactions Leading to Cyclopentanes, Cyclopentenes; General Cyclopentane Ring Synthesis

(b) Cyclopentanes and Cyclopentenes by Cycloaddition Reactions

(c) Cyclopentanes and Cyclopentenes by Ring Expansion and Ring Contraction Processes

(d) Cyclopentanones and Cyclopentenones by Cyclisation Processes

(e) Cyclopentanones and Cyclopentenones by Cycloaddition Reactions

(F) Cyclopentanones and Cyclopentenones by Ring Expansion and Ring Contraction Reactions

(G) Cyclopentanones and Cyclopentenones by Rearrangements and by Miscellaneous Reactions


3. Reactions

(a) Cyclopentanes, Cyclopentenes, and Simple Derivatives

(b) Cyclopentanones, Cyclopentenones, and Derivatives

Chapter 4b. Natural Products Containing the Cyclopentane Sub-Unit: Prostaglandins


1. Introduction


2. Structure and Nomenclature


3. Prostaglandin Biosynthesis

(a) Mammalian Biosynthesis

(b) Non-Mammalian Biosynthesis


4. Prostaglandin Total Synthesis

(a) Corey's Bicyclic Lactone Approach

(b) Approaches via Polycyclic Intermediates

(c) Conjugate Addition and Three Component Coupling Approaches

(d) Recent Synthetic Approaches to PGs

(e) PG Metabolism and Analogue Synthesis

(F) Synthesis of Non-mammalian Prostanoids


5. Bibliography

(a) General and Biological

(b) Synthetic

Chapter 4c. Cyclopentadiene


1. Introduction


2. Preparation of σ-Bonded Cyclopentadiene Derivatives

(a) Deuteriated Cyclopentadiene

(b) Alkyl Substituents

(c) Cyano, Carbonyl, Carboxyl and Trifluoromethyl Substituents

(d) Phosphine Substituents

(e) Other Substituents


3. Ionic Metal Derivatives


4. Fluxionality of Cyclopentadienyl Derivatives


5. Metal Complexes - Structure and Reactions

(a) The Cyclopentadienyl Ligand

(b) Monoligating Cyclopentadienyl Complexes

(c) Bridged Biscyclopentadiene Complexes

(d) Bifunctional Cyclopentadienyl Ligands


6. Metal Complexes - Applications


7. Reactions of Cyclopentadiene

Chapter 5a. Cyclohexane and Its Derivatives

Introduction


1. Cyclohexane

(a) Synthesis


2. Halogenocyclohexanes

(a) Fluorocyclohexane and Derivatives

(b) Chlorocyclohexane

(c) Bromocyclohexane

(d) Halogenocyclohexanes through Addition to Benzene Rings


3. Cyclohexadienyl Intermediates

(a) Cyclohexadienyl Radical

(b) Muonium Attack

(c) Cyclohexadienylium Ion


4. Cyclohexanol and Cyclohexanone

(a) Synthesis


5. Cyclohexadienones and Derivatives

(a) Identification and Preparation


6. Cyclohexanamine (Cyclohexylamine)

Chapter 5b. Natural Products Containing a Cyclohexane, Cyclohexene, or Cyclohexadiene Subunit


1. Simple Examples

(a) Nonfunctionalized

(b) Functionalized


2. Nonfunctionalized or Unusual Terpenoids

(a) Mono Terpenoids

(b) Nonfunctionalized Sesquiterpenes

(c) Norsesquiterpenes

(d) Furanoterpenes

(e) Oxygenated Norterpenoids

(F) Rearranged or Unusual Terpenoids


3. C13 Norterpenoids


4. Flavonoid, Chalcone, and Coumarin Types


5. Shikimic Acid Pathway

(a) Mechanistic Aspects

(b) Synthesis

(c) Natural Occurrence


6. Cyclitols

(a) Natural Occurrence

(b) Synthesis

(c) Cyclitol Epoxides


7. Inositols

(a) Natural Occurrence

(b) Synthesis


8. Pseudosugars

(a) Natural Occurrence

(b) Synthesis


9. Aminocyclitols

(a) Natural Occurrence

(b) Synthesis


10. Benzoquinones


11. Quinols


12. Halogenated Tyrosine Metabolites


13. Concluding Remarks

Chapter 5c. Cyclohexadienes


1. Introduction


2. Preparation of Cyclohexadienes

(a) Metal-Ammonia (Birch) Reduction of Aromatic Compounds

(b) Microbial Oxidation of Aromatic Compounds

(c) Cyclohexadienes from Cyclohexenones


3. Reactions of Cyclohexadienes

(a) Conjugation of 1,4-Cyclohexadienes

(b) Cycloaddition Reactions

(c) Palladium-Catalyzed 1,4-Difunctionalization


4. Metal Complexes of Cyclohexadienes

(a) Cyclohexadiene-Fe(CO)2L Complexes

(b) Cyclohexadiene-CoCp Complexes and the Derived Cyclohexadienyl-CoCp Cations

(c) Cyclohexadiene-Mo(CO)2Cp and Related Complexes

Guide to the Index

Index