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Table of Contents

Chapter 1     Protecting Groups: An Overview

Chapter 2     Carbonyl Protecting Groups

Chapter 3     Diol Protecting Groups

Chapter 4     Hydroxyl Protecting Groups

Chapter 5     Thiol Protecting Groups

Chapter 6     Carboxyl Protecting Groups

Chapter 7     Phosphate Protecting Groups

Chapter 8     Amino Protecting Groups

Epilogue:      Problems, Problems, Problems...

Chapter 1     Protecting Groups: An Overview

1.1     Death, Taxes, and Protecting Groups

1.2     Deprotection: The Concept of Orthogonal Sets
1.2.1  Protecting Groups Cleaved by Basic Solvolysis
1.2.2  Protecting Groups Cleaved by Acid
1.2.3  Protecting Groups Cleaved by Heavy Metals
1.2.4  Protecting Groups Cleaved by Fluoride Ions
1.2.5  Protecting Groups Cleaved by Reductive Elimination
1.2.6  Protecting Groups Cleaved by β-Elimination
1.2.7  Protecting Groups Cleaved by Hydrogenolysis
1.2.8  Protecting Groups Cleaved by Oxidation
1.2.9  Protecting Groups Cleaved by Dissolving Metal Reduction
1.2.10 Protecting Groups Cleaved by Nucleophilic Substitution
1.2.11 Protecting Groups Cleaved by Transition Metal Catalysis
1.2.12 Protecting Groups Cleaved by Light
1.2.13 Protecting Groups Cleaved by Enzymes

1.3     Relay Deprotection

1.4     Transprotection

1.5     Mutual Protection

1.6     Temporary Protection

1.7     Protecting Groups As Not-So-Innocent Bystanders
1.7.1  Neighbouring Group Participation
1.7.2  Conformation and Electronic Effects
1.7.3  Co-ordination Effects

1.8     Protecting Groups and Solid-Phase Synthesis

1.9     Reviews
1.9.1  General Reviews on Protecting Groups
1.9.2  Reviews on Enzyme-Labile Protecting Groups
1.9.3  Reviews on Photo-Labile Protecting Groups
1.9.5  Reviews on Linkers in Solid-Phase Synthesis
1.9.4  Reviews on the Synthesis of Complex Targets Including Discussion of Protecting Group Problems and Strategies.

References

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Chapter 2     Carbonyl Protecting Groups

2.1     Introduction

2.2     O,O-Acetals
2.2.1  Cyclic Acetals
2.2.2  O,O-Acetals in Asymmetric Synthesis
2.2.3  Acyclic Acetals

2.3     S,S-Acetals

2.4     O,S-Acetals

2.5     N,O-Acetals

2.6     Cyanohydrins

2.7     Orthoester Derivatives
2.7.1  O,O,O-Orthoesters
2.7.2  O,S,S-Orthoesters
2.7.3  S,S,S-Orthoesters

2.8     Oxazolines

2.9     Reviews

References

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Chapter 3     Diol Protecting Groups

3.1     Introduction

3.2     O,O-Acetals
3.2.1  Isopropylidene Acetals (Acetonides)
3.2.2  Cyclohexylidene and Cyclopentylidene Acetals
3.2.3  The Arylmethylene Acetal Family
3.2.4  Methylene Acetals
3.2.5  Diphenylmethylene Acetals

3.3     1,2-Diacetals
3.3.1  Dispiroketal (Dispoke) Derivatives
3.3.2  Cyclohexane-1,2-diacetals
3.3.3  Butane-2,3-diacetals

3.4     Silylene Derivatives

3.5     1,1,3,3-Tetraisopropyldisiloxanylidene Derivatives

3.6     N,O-Acetals

3.7     Reviews
3.7.1  Reviews Concerning the Preparation of Acetals and Their Use as Protecting Groups
3.7.2  Reviews Concerning Acetal Derivatives of Carbohydrates
3.7.3  Reviews Concerning 1,2-Diacetals
3.7.4  Reviews Concerning N,O-Acetals

References

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Chapter 4     Hydroxyl Protecting Groups

4.1     Introduction

4.2     Silyl Ethers
4.2.1  Trimethylsilyl Ethers
4.2.2  Triethylsilyl Ethers
4.2.3  tert-Butyldimethylsilyl Ethers
4.2.4  tert-Butyldiphenylsilyl Ethers
4.2.5  Tri-isopropylsilyl Ethers
4.2.6  Diethylisopropylsilyl Ethers
4.2.7  Thexyldimethylsilyl Ethers
4.2.8  Triphenylsilyl Ethers
4.2.9  Di-tert-butylmethylsilyl Ethers

4.3     Alkyl Ethers
4.3.1  Methyl Ethers
4.3.2  tert-Butyl Ethers
4.3.3  Benzyl Ethers
4.3.4  p-Methoxybenzyl and 3,4-Dimethoxybenzyl Ethers
4.3.5  Trityl Ethers
4.3.6  Allyl Ethers

4.4     Alkoxymethyl Ethers
4.4.1  Methoxymethyl Ethers
4.4.2  2-Methoxyethoxymethyl Ethers
4.4.3  Benzyloxymethyl Ethers
4.4.4  p-Methoxybenzyloxymethyl Ethers
4.4.5  2-(Trimethylsilyl)ethoxymethyl Ethers

4.5     Tetrahydropyranyl and Related Ethers

4.6     Methylthiomethyl Ethers

4.7     Esters

4.8     Carbonates
4.8.1  Benzyl Carbonates
4.8.2  p-Nitrobenzyl Carbonates
4.8.3  tert-Butyl Carbonates
4.8.4  2,2,2-Trichloroethyl Carbonates
4.8.5  2-(Trimethylsilyl)ethyl Carbonates
4.8.6  Allyl Carbonates

4.9     Reviews
4.9.1  General Reviews Concerning the Protection of Hydroxyls
4.9.2  Reviews Concerning Enzyme-Mediated Esterification and Hydrolysis of Esters
4.9.3 Reviews Concerning Organosilicon Chemistry Relevant to Hydroxyl Protection

References

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Chapter 5     Thiol Protecting Groups

5.1     Introduction

5.2     Thioether Derivatives
5.2.1  tert-Butyl Thioethers
5.2.2  Benzyl and Substituted Benzyl Thioethers
5.2.3  Triphenylmethyl Thioethers
5.2.4  2-(Trimethylsilyl)ethyl Thioethers
5.2.5  2-Cyanoethyl Thioethers
5.2.6  9-Fluorenylmethyl Thioethers

5.3     Thiocarbonate Derivatives

5.4     Disulfides as Protecting Groups and Targets

5.5     Reviews
5.5.1  Reviews Concerning the Protection of Thiols
5.5.2  Reviews Concerning the Chemistry of Thiols and Disulfides

References

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Chapter 6     Carboxyl Protecting Groups

6.1     Introduction

6.2     General Comments on the Esterification of Carboxylic Acids

6.3     Methyl Esters and Derivatives
6.3.1  Methyl Esters
6.3.2  tert-Butyl Esters
6.3.3  Benzyl Esters
6.3.4  Allyl Esters
6.3.5  Phenacyl Esters

6.4     Alkoxyalkyl Esters

6.5     Esters Cleaved by β-Elimination
6.5.1  2,2,2-Trichloroethyl Esters
6.5.2  2-(Trimethylsilyl)ethyl Esters
6.5.3  2-Tosylethyl Esters and Related Base-Labile Groups

6.6     Silyl Esters

6.7     Reviews
6.7.1  Reviews Concerning the Specific Use of Esters as Protecting Groups
6.7.2  Reviews Concerning the Preparation of Esters
6.7.3  Reviews Concerning Techniques for Facilitating Esterification
6.7.4  Reviews Concerning the Use of Allyl Esters in Carboxyl Protection
6.7.5  Reviews Concerning the Nucleophilic Cleavage of Esters

References

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Chapter 7     Phosphate Protecting Groups

7.1     Introduction

7.2     The Reaction of Phosphate Esters with Nucleophiles

7.3     Methyl Esters and Derivatives
7.3.1  Methyl and Isopropyl Esters
7.3.2  tert-Butyl Esters
7.3.3  Benzyl and p-Methoxybenzyl Esters
7.3.4  Allyl Esters
7.3.5  3',5'-Dimethoxybenzoin Esters
7.3.6  p-Hydroxyphenacyl Esters

7.4     Esters Cleaved by β-Elimination
7.4.1  2-Cyanoethyl Esters
7.4.2  9-Fluorenylmethyl Esters
7.4.3  2-(Trimethylsilyl)ethyl Esters
7.4.4  2-(Methylsulfonyl)ethyl Esters and Related Base-Labile Groups
7.4.5  2,2,2-Trichloroethyl Esters

7.5     Reviews
7.5.1  Reviews Concerning Protection for the Phosphate Group
7.5.2  Reviews Concerning the Mechanism of Nucleophilic Substitution in Phosphate Esters

References

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Chapter 8     Amino Protecting Groups

8.1     Introduction

8.2     Imide and Amide Derivatives
8.2.1  Phthalimidoyl and Tetrachlorophthalimidoyl
8.2.2  Dithiasuccinoyl
8.2.3  Trifluoroacetyl
8.2.4  Relay Deprotection of N-Acyl Derivatives

8.3     Carbamate Derivatives
8.3.1  Methoxy- and Ethoxycarbonyl
8.3.2  tert-Butoxycarbonyl
8.3.3  Benzyloxycarbonyl
8.3.4  Allyloxycarbonyl
8.3.5  9-Fluorenylmethoxycarbonyl
8.3.6  2-(Trimethylsilyl)ethoxycarbonyl
8.3.7  2,2,2-Trichloroethoxycarbonyl

8.4     Sulfonyl Derivatives
8.4.1  Arylsulfonyl
8.4.2  2-(Trimethylsilyl)ethylsulfonyl

8.5     Sulfenyl Derivatives

8.6     Alkyl Derivatives
8.6.1  N,O-Acetals
8.6.2  Triazones
8.6.3  Benzyl and Diphenylmethyl
8.6.4  Trityl and 9-Phenylfluorenyl
8.6.5  Allyl

8.7     Silyl Derivatives

8.8     Imine Derivatives
8.8.1  Bis(methylthio)methylene
8.8.2  Diphenylmethylene

8.9     Special Cases
8.9.1  Orthogonal Protecting Groups for the Synthesis of Polyamines
8.9.2  Protecting Groups for Guanidines
8.9.3  Protecting Groups for Indoles, Pyrroles and Imidazoles

8.10     Reviews
8.10.1  General Reviews on Amino Protecting Groups
8.10.2  Reviews Concerning N-Protection in the Synthesis of α-Amino Aldehydes and Ketones
8.10.3  Reviews Concerning N-Protection in the Synthesis of β-Lactams
8.10.4  Reviews Concerning N-Functional Groups Pertinent to Their Role as Protecting Groups
8.10.5  Reviews Concerning the Synthesis of Natural Guanidine Derivatives
8.10.6  Reviews Concerning the Synthesis of Natural Polyamines

References

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Epilogue: Problems, Problems, Problems...

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