Preparation of Aryl- and Heteroaryltrimethylsilanes

This review presents a comprehensive survey of the synthetic methods for aryl- and heteroaryltrimethylsilanes. Their preparation can result from direct silicon-carbon coupling reactions, from cycloaddition reactions, or through modification of silylaromatic or -heteroaromatic compounds by incorporation of further functional groups or by conversion of substituents already present. 1. Introduction 2. Direct Introduction of Trimethylsilyl Groups into Aromatic and Heteroaromatic Compounds 2.1. Radical Silylation of Aromatic and Heteroaromatic Compounds 2.2. Nucleophilic Silylation of Aromatic and Heteroaromatic Compounds 2.3. Electrophilic Silylation of Aromatic and Heteroaromatic Compounds 3. Synthesis of Aryl- and Heteroaryltrimethylsilanes via Cycloaddition Reactions 3.1. Aryltrimethylsilanes via [2+2+2]Cycloaddition Reactions 3.2. Aryl- and Heteroaryltrimethylsilanes via [4+2]Cycloaddition Reactions 3.3. Heteroaryltrimethylsilanes via [2+3]Cycloaddition Reactions 4. Introduction of Substituents into the Nucleus of Aryl- and Heteroaryltrimethylsilanes 4.1. Halogenation 4.2. Introduction of Sulfur Functions 4.3. Introduction of Nitrogen Functions 4.4. Introduction of Phosphorus Functions 4.5. Alkylation and Hydroxyalkylation 4.6. Acylation 4.7. Carboxylation 4.8. Silylation 4.9. Protonation 5. Transformation of Substituents in Aryl- and Heteroaryltrimethylsilanes 5.1. Nucleophilic Exchange of Halides 5.2. Functionalization of Carboxylic Acid Derivatives 5.3. Functionalization of Hydroxy and Amino Groups 5.4. Condensation Reactions 5.5. Oxidation Reactions 5.6. Reduction Reactions 5.7. Metal Complexes of Aryl- and Heteroaryltrimethylsilanes 5.8. Miscellaneous 6. Conclusions