The Carbohydrates Volume 1A

The Carbohydrates Volume 1A

Chemistry and Biochemistry

2nd Edition - May 28, 1972

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  • Author: Ward W Pigman
  • eBook ISBN: 9780323138338

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Description

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

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