The Carbohydrates Volume 1A, Volume 1A

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.

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)