
The Carbohydrates Volume 1A
Chemistry and Biochemistry
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The Carbohydrates: Chemistry and Biochemistry, Second Edition, Volume IA deals with the chemical and biochemical aspects of carbohydrates such as monosaccharides, sugars, esters, halogen derivatives, phosphates, glycosides, glycosans, alditols, and cyclitols. Topics range from carbohydrate chemistry and stereochemistry to the synthesis of naturally occurring monosaccharides, mutarotations and actions of acids and bases, conformations of sugars, and reactivity of saccharide hydroxyl groups toward esterification. This book consists of 15 chapters that explore the effects of ionizing radiations and autoxidation reactions, physical methods and methods of separation, nucleosides and antibiotics, and the biosynthesis of sugars and complex saccharides. The rapidly growing fields of glycolipids and glycoproteins are also discussed. In addition, the reader is introduced to halogen derivatives such as glycosyl halides and nonanomeric halides, along with the hydrolysis and synthesis of phosphates and other inorganic esters, determination of the structure of glycosides, and the physical and chemical properties of acyclic derivatives. The two final chapters cover the official nomenclature rules for carbohydrates and for enzymes having carbohydrates as substrates. This book will be of interest to chemists and biochemists.
Table of Contents
List of Contributors
Preface
Contents of Other Volumes
Errata
1. 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
References
2. 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
References
3. 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
References
4. 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
References
5. 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
References
6. 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
References
7. Halogen Derivatives
I. Introduction
II. Glycosyl Halides
A. General Considerations
B. Synthesis
C. Reactivity
III. Nonanomeric Halides
A. General Considerations
B. Synthesis
C. Reactivity
References
8. 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
References
9. 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
References
10. 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
References
11. 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
References
12. 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
References
13. 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
References
4. 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
References
15. 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
References
Author Index (Volume IA)
Subject Index (Volume IA)
Product details
- No. of pages: 642
- Language: English
- Copyright: © Academic Press 1972
- Published: May 28, 1972
- Imprint: Academic Press
- eBook ISBN: 9780323138338
About the Author
Ward W Pigman
Affiliations and Expertise
Corn Products Refining Co. Argos, Illnois formerly with ational Bureau of Standards