Hard and Soft Acids and Bases Principle in Organic Chemistry

Preface


1 Introduction

1.1. Definitions of Acids and Bases

1.2. The Hard and Soft Acids and Bases (HSAB) Concept: Historical Development

References


2 Classification of Hard and Soft Acids and Bases

2.1. Pearson's Generalization

2.2. Softness Scales

2.3. Theoretical Descriptions of HSAB

References


3 Chemical Reactivity

3.1. Stability of Organic Compounds and Complexes

3.2. Symbiosis

3.3. Intrinsic Strength

References


4 Displacement Reactions

4.1. General Mechanisms

4.2. Nucleophilic Reactivity

4.3. Formation and Cleavage of O-Alkyl Bond of Carboxylic Esters

4.4. Multicentered Reactions: Saville's Rules

4.5. Ambident Reactivity

References


5 Alkene Chemistry

5.1. Formation of Olefinic Linkages by Elimination Reactions. Elimination vs. Substitution

5.2. Addition to Double Bonds

5.3. Oxidation

5.4. Miscellaneous Reactions

References


6 Aromatic and Heterocyclic Chemistry

6.1. Exchange Reactions

6.2. Electrophilic Substitutions

6.3. Nucleophilic Substitutions

6.4. Ambident Behavior of Heterocyclic Compounds

6.5. Aromatic Claisen Rearrangements

6.6. Oxidative Coupling of Phenols

References


7 Reactivity of Carbonyl Compounds

7.1. The Carbonyl Group as a Hard Acceptor and a Hard Donor

7.2. The Carbonyl Oxygen as a Soft Acceptor

7.3. Reactions of α,β-Unsaturated Carbonyl Compounds

7.4. Aspects of Some Carboxylic Acid Derivatives

7.5. Some Carbonyl-Forming Processes

References


8 Organophosphorus Reactions

8.1. General Considerations

8.2. Trivalent Phosphorus Compounds as Nucleophiles

8.3. Nucleophilic Attack on the Phosphorus Center

References


9 Reactions of Organosulfur Compounds and Other Chalcogenides

9.1. Chemical Selectivity of Organic Chalcogenides

9.2. Divalent Sulfur Compounds as Soft Donors

9.3. Divalent Sulfur Compounds as Soft Acceptors

9.4.Chemistry of the Sulfinyl Group

9.5. Reactions of Higher Valent Sulfur Derivatives

References


10 Organoboron Chemistry

10.1. Stability of Organoboranes. Exchange Reactions

10.2. Hydroboration

10.3. Reactions of Arylboron Compounds

10.4. Some Aspects of Organoaluminum Reactions

References


11 Other Applications of the HSAB Principle

11.1. Solubility and Protonation

11.2. Carbenes and Nitrenes

11.3. Organic Chemistry of Group IV Elements

11.4. Reactions of Organohalides, Grignard and Related Reagents

11.5. Exceptions

References

Addendum

Author Index

Subject Index