The Carbohydrates Volume 1A

List of ContributorsPrefaceContents of Other VolumesErrata1. Introduction: Structure and Stereochemistry of the Monosaccharides I. General Relations II. Some Definitions III. Nomenclature IV. Development of Carbohydrate Chemistry V. Structures of D-Glucose and D - Fructose VI. Stereochemistry A. General Principles B. Establishment of the Configuration of D-Glucose and Some Other Sugars C. D and L Nomenclature D. Conformational Representation of Acyclic Sugar Derivatives VII. Ring Structures of the Sugars A. Necessity for Ring Structures B. Proof of Ring Structure C. Configuration at the Anomeric Carbon Atom D. Depiction of the Ring Structures of the Sugars E. Nomenclature of Anomers (α,β Nomenclature) VIII. Homomorphous Sugars A. Homomorphology B. Nomenclature for Higher Sugars and for Compounds Having Numerous Asymmetric Atoms in a Carbon Chain IX. Conformational Representation of Cyclic Sugars References2. Occurrence, Properties, and Preparation of Naturally Occurring Monosaccharides (Including 6-Deoxy Sugars) I. Introduction A. Structures of the Natural Monosaccharides B. Monosaccharides in Nature II. Naturally Occurring Monosaccharides A. Preparation and Isolation B. Properties and Identification C. The Monosaccharides References3. Synthesis of Monosaccharides I. Introduction II. Total Synthesis A. The Formose Reaction B. Synthesis from Alkene and Alkyne Derivatives III. Ascent of the Series A. The Fischer-Kiliani Cyanohydrin Synthesis B. The Nitromethane Synthesis C. The Diazomethane Synthesis D. Syntheses Based on Malonic Esters and Related Compounds E. The Wittig Reaction F. Ethynylation G. Aldol Condensation Reaction IV. Descent of the Series A. The Ruff Degradation B. The Wohl Degradation C. The Weerman Degradation D. The Disulfone Method E. Controlled Oxidation with Glycol-Cleaving Reagents F. The Hunsdiecker Reaction G. Other Methods V. Changes in Configuration at Asymmetrically Substituted Carbon Atoms A. Base-Catalyzed Epimerizations and Isomerizations B. Replacement Reactions of Sulfonic Esters C. Molecular Inversion D. Sequential Oxidation and Reduction E. Inversion of Configuration by Way of Carboxylic Ester Derivatives VI. Synthesis from Unsaturated Derivatives A. Hydroxylation B. Hydroboration VII. Oxidation of Alditols A. Chemical Methods B. Biological Methods VIII. Isotopically Labeled Carbohydrates A. Carbon-14 Labeling B. Tritiated Carbohydrates C. Deuterium-Labeled Carbohydrates References4. Mutarotations and Actions of Acids and Bases I. Mutarotations and Changes Occurring in the Absence of Strong Acids and Bases A. Introduction B. Kinetics C. Composition of Solutions D. Mechanisms E. Mutarotase II. Action of Acids and Alkalies A. Enolization B. Beta Elimination C. Further Action of Acids D. Further Action of Alkalies References5. Conformations of Sugars I. Introduction II. Determination of Conformations A. Complexing with Cuprammonia B. X-Ray Crystal Structure Analysis C. Infrared Spectroscopy D. Optical Rotation E. Nuclear Magnetic Resonance Spectroscopy III. Calculation of Conformational Free Energies A. Nonbonded Interaction Energies B. The Anomeric Effect C. Conformational Free Energies IV. The Conformations of Pyranoses A. In Aqueous Solution B. The Effect of Solvents and Substituents V. The Conformations of Furanoses VI. Sugars Having Fused Rings and Unsaturated Sugars VII. Acyclic Sugar Derivatives References6. Esters I. Introduction II. Reactivity of Saccharide Hydroxyl Groups toward Esterification III. Acetates A. Formation B. Deacetylation C. Analysis IV. Ortho Esters V. Benzoates VI. Esters of Other Carboxylic Acids VII. Partially Esterified Sugar Structures VIII. Migration of Acyl Groups IX. Mixed Esters X. Carbonates and Thiocarbonates XI. Sulfonates References7. Halogen Derivatives I. Introduction II. Glycosyl Halides A. General Considerations B. Synthesis C. Reactivity III. Nonanomeric Halides A. General Considerations B. Synthesis C. Reactivity References8. Phosphates and Other Inorganic Esters I. Phosphate Esters A. Synthesis of Phosphate Esters B. Phosphate Migration C. Hydrolysis of Phosphates D. Separation and Detection of Phosphates E. Specific Rotations of Natural and Synthetic Carbohydrate Phosphates II. Borate Esters III. Nitrate Esters IV. Sulfate Esters V. Glycosyl Azides References9. Glycosides I. Introduction II. Methods for Synthesis A. Fischer Method B. From Acetals and Thioacetals C. Anomeric Replacements D. Other Methods III. Determination of the Structure of Glycosides IV. Properties of Glycosides V. Reactions Involving the Glycosidic Linkage A. Anomerization B. Acidic Hydrolysis C. Alkaline Hydrolysis D. Hydrogenolysis E. Chlorinolysis F. Photolysis and Radiolysis VI. 1-Thioglycosides A. Preparation B. Reactions References10. Acyclic Derivatives I. Introduction II. Dithioacetals A. Formation B. Reactions III. Monothioacetals IV. Acetals V. Aldehydo Structures A. Formation B. Aldehydrol Derivatives VI. Acyclic Aldonic Acid Derivatives VII. Keto Structures A. Formation B. Reactivity of Diazomethyl Ketones C. Acyclic Diketose Structures VIII. Glycosuloses IX. General Properties of Acyclic Derivatives A. Physical Properties B. Chemical Properties X. Acyclic Forms in Aqueous Solution References11. Cyclic Acetal Derivatives of Sugars and Alditols I. Formation of Cyclic Acetals II. Cyclic Acetals from Acyclic Sugar Derivatives A. With Aldehydes B. With Ketones III. Cyclic Acetals from Cyclic Sugar Derivatives A. Formation B. Applications in Synthesis References12. Ethers of Sugars I. Types of Sugar Ethers and Their Occurrence II. The Removal of Ether Groups III. Methods for Synthesis of Partially Methylated Sugars A. Methylation Procedures B. Use of Acyclic Derivatives C. Methylation Reagents D. Methylation of Acidic and Basic Sugars IV. Ethers of Sugars of Low Molecular Weight A. Ethers of Trioses and Aldonic Acids B. Ethers cfTetroses C. Ethers of Pentoses References13. Glycosans and Anhydro Sugars I. Introduction II. Glycosans A. 1,2-Anhydropyranoses B. 1,3-Anhydropyranoses C. 1,4-Anhydropyranoses (1,5-Anhydrofuranoses) D. 1,6-Anhydropyranoses E. 1,6-Anhydrofuranoses F. Miscellaneous Aldosans G. Ketose Derivatives III. Anhydro Sugars A. Introduction B. Synthesis of Anhydro Sugars C. Epoxides D. Anhydro Sugars of the Tetrahydrofuran Type E. Miscellaneous Anhydro Sugars IV. Rearrangements of Anhydro Sugars A. Conversion of Epoxides into 3,6-Anhydro Derivatives B. Interconversion of Epoxide and Oxetane Systems C. Epoxide Migrations References4. Alditols and Derivatives I. Introduction II. Configurations, Occurrence, and Preparation A. Tetritols B. Pentitols C. Hexitols D. Heptitols E. Octitols F. Nonitols and Decitols III. Synthesis A. Miscellaneous Methods B. Catalytic Isomerization of Alditols IV. Proofs of Structure and Configuration V. Reactions A. Esterification B. Periodate Oxidation C. Oxidation D. Reduction E. Etherification and Acetalation VI. Qualitative and Quantitative Determination VII. Monodeoxy Derivatives VIII. Biochemistry References15. The Cyclitols I. Introduction A. Nomenclature II. The Inositols (Cyclohexanehexols) and Their O-Substitution Products A. The Major Naturally Occurring Inositols (myo, D- and L-chiro, scyllo) B. The Other Inositols (epi, muco, allo, neo, eis) C. Methyl Ethers of Inositols D. Quantitative Determination of Cyclitols E. Inositol Phosphates, Lipids, and Glycosides F. Oxidation with Periodate and Nitric Acid G. Biochemistry III. Cyclitols and Conformational Analysis A. Nonbonded Interaction Energies B. Use of Proton Magnetic Resonance Spectroscopy C. Optical Rotation IV. Methods for the Total Synthesis of Cyclitols A. Synthesis from Smaller Molecules B. The "Benzeneglycol" Synthesis C. The Nitroinositol Synthesis V. Reactive Cyclitol Derivatives A. Selective Blocking B. Sulfonic Esters C. Anhydroinositols D. Deoxyhaloinositols E. Thioinositols VI. Cyclitol Ketones (Inososes) VII. The Lower Cyclitols A. The Cyclohexanepentols B. The Cyclohexenetetrols C. The Cyclohexanetetrols and Triols D. Cyclopentane Cyclitols VIII. Aminocyclitols (Inosamines) IX. Cyclitols Having Side Chains A. With C-Methyl and Substituted C-Methyl Groups B. Cyclitol Carboxylic Acids X. Cyclitol Reactions of General Significance in Carbohydrate Chemistry A. Formation of Cyclic Acetals B. Acyl Migration C. Epimerization D. Epoxide Migration ReferencesAuthor Index (Volume IA)Subject Index (Volume IA)