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1 Fundamental Considerations.- 2 Chemistry of Trimethylsilyl Cyanide.- 2.1 Introduction.- 2.2 Addition of Trimethylsilyl Cyanide to Polar Multiple Bonds.- 2.3 Utility of Trimethylsilyl Ethers of Cyanohydrins.- 2.4 Acyl Substitution Reactions of Trimethylsilyl Cyanide.- 2.5 Reactions of Trimethylsilyl Cyanide with Polar Cumulenes.- 2.6 Substitution Reactions of Trimethylsilyl Cyanide.- 2.7 Synthesis of Trimethylsilyl Cyanide.- 3 Trimethylsilyl Iodide and Bromide.- 3.1 Introduction.- 3.2 Cleavage of Ethers.- 3.3 Cleavage of Acetals and Ketals.- 3.4 Conversion of Alcohols and Alkoxytrimethylsilanes to Alkyl Iodides.- 3.5 Reaction of TMS-Br with Alcohols.- 3.6 Reaction of Oxiranes with TMS-I-Conversion to Allylic Alcohols.- 3.7 Hydrolysis of Esters.- 3.8 Hydrolysis of Carbamates.- 3.9 Hydrolysis of Dialkyl Phosphonates.- 3.10 Preparation of ?-and ?-Iodo Ketones.- 3.11 Preparation of TMS-Br and TMS-I.- 4 Silyl Azides.- 4.1 Introduction.- 4.2 Preparation and Properties of Organosilyl Azides.- 4.3 Cycloaddition Reactions.- 4.4 Reactions with Aldehydes or Ketones.- 4.5 Reactions with Epoxides.- 4.6 Reactions with Cumulenes.- 4.7 Reactions with Phosphines.- 4.8 Reactions with Grignard Reagents.- 4.9 Reactions with Acid Chlorides or Anhydrides.- 4.10 Reactions with Lead Tetraacetate or Phenyliodosodiacetate.- 5 Silyl Nitronates.- 5.1 Introduction-Physical and Spectroscopic Properties.- 5.2 Cycloaddition Reactions.- 5.3 Nitro-Aldol Reactions.- 5.4 Oxidation.- 5.5 Preparation.- 6 Peterson Reaction.- 6.1 Introduction.- 6.2 ?-Silyl Organometallics.- A. ?-Silyl Grignard and Organolithium Reagents.- B. Halogen-Metal Exchange.- C. Addition of Organometallics to Vinyl Silanes.- D. Metallation.- E. Displacement Reactions.- 6.3 Stereochemical Control of Elimination.- 6.4 Preparation of Substituted Alkenes.- A. Ketene Thioacetals.- B. Vinyl Sulfoxides.- C. Thio Enol Ethers.- D. Sulfines.- E. Allenes.- F. Vinyl Silanes.- G. Vinyl Boronic Esters.- H. Cross Aldol Reaction-?,?-Unsaturated Aldehydes.- I. ?,?-Unsaturated Carboxylic Acids.- J. ?,?-Unsaturated Nitriles.- K. ?,?-Unsaturated Esters.- L. ?-Ylidene-?-butyrolactones.- M. Silyl Reformatsky Reaction.- N. ?,?-Unsaturated Thiol Esters.- O. ?,?-Unsaturated Amides.- P. Imines.- 6.5 Related Reactions.- 7 Vinyl Silanes.- 7.1 Introduction.- 7.2 Elimination of Trimethylhalosilanes from ?-Halosilanes.- 7.3 Stereospecificity of Elimination.- 7.4 Electrophilic Substitution Reactions.- A. Halogens.- B. Reactions of ?-Trimethylsilyl Epoxides with Electrophiles.- C. ?-Sily1 Styrenes.- D. Protodesilylation of Vinyl Silanes.- E. Friedel-Crafts Acylation Reactions.- F. Friedel-Crafts Alkylation.- G. Sulfenyl Halides.- H. Palladium Chloride.- 7.5 Addition of Carbanions to Vinyl Silanes.- 7.6 Masked Carbonyl Groups.- 7.7 1,2-Transposition of Carbonyl Groups.- 7.8 Cycloaddition Reactions.- 7.9 Preparation of Vinyl Silanes.- A. E-1-Trimethylsilyl-1-alkenes.- B. Z-1-Trimethylsilyl-1-alkenes.- C. 2-Trimethylsilyl-1-alkenes.- D. 1-Cycloalkenyltrimethylsilanes.- E. E- and Z-1,2-Dialkyl-l-trimethylsilyl ethylenes.- F. 1,2-Disub stituted- 1,2- bis(trimethylsilyl)ethylene, 1,1-Di substituted-2,2-bis(trimethylsilyl)ethylenes and 1,1,2-Trisubstituted-2-trimethylsilyl ethylenes.- 8 Aryl Silanes.- 8.1 Introduction.- 8.2 Protodesilylation.- 8.3 Halodesilylation.- 8.4 Metallo-desilylation.- 8.5 Sulfo-desilylation.- 8.6 Acyl-desilylation.- 8.7 Alkyl-desilylation.- 8.8 Diazo-desilylation.- 8.9 Nitrodesilylation.- 8.10 Aryl Silanes as Organometallic Reagents.- 8.11 Preparation.- 9 Silyl Acetylenes.- 9.1 Introduction.- 9.2 Addition Reactions.- 9.3 Electrophilic Substitution.- A. Protic Acids.- B. Halogens.- C. Acyl Chlorides.- D. Sulfonyl Chlorides-Sulfur Trioxide.- E. Aldehydes and Ketones.- F. Carbocations.- 9.4 Protection of Terminal Alkynes.- 9.5 Cycloaddition Reactions.- A. Diels-Alder Reactions.- B. Silyl-ynamines.- C. Cobalt-Catalyzed Cycloadditions.- D. [2 + 2] and [2 + 3] Cycloadditions.- 9.6 Preparation of Silylacetylenes.- A. 1-Trialkylsilylalkynes.- B. 1-Trialkylsilyl-2-alkynes.- C. 1-Trialkylsilyl-1,2-dienes.- D. 1-Trimethylsilyl-2,3-dienes.- 10 Tetraalkylsilanes, Alkylpentafluorosilicates and Alkenylpentafluorosilicates.- 10.1 Introduction.- 10.2 Electrophilic Cleavage of Tetraalkylsilanes.- A. Protic Acids.- B. Acylium Ions.- C. Carbocations.- D. Halogens.- E. Trimethylsilyl Chlorosulfonate.- 10.3 Preparation.- 10.4 Alkylpentafluorosilicates.- 10.5 Reaction of Alkylpentafluorosilicates with Halogens.- 10.6 Reaction with m-Chloroperbenzoic Acid.- 10.7 Reaction with TCNE.- 10.8 Reduction.- 10.9 Exchange.- 10.10 Alkenylpentafluorosilicates.- 10.11 Electrophilic Cleavage of Alkenylpentafluorosilicates.- 11 Allylic Silanes.- 11.1 Introduction.- 11.2 Electrophilic Substitution.- A. Protic Acids.- B. Halogens.- C. Acid Chlorides.- D. Sulfonyl Chlorides.- E. Transition Metal Complexes.- F. Sulfenyl Halides.- G. Carbocations.- H. Ketones, Aldehydes, Acetals, and Ketals.- I. ?,?-Unsaturated Ketones and Aldehydes.- J. ?-Nitro Alkenes.- K. ?-and ?-Keto Acetals and ?-Keto Esters.- 11.3 Cycloaddition Reactions of Allylic Silanes.- A. [2 + 2] Cycloaddition Reactions.- B. [3 + 2] Cycloaddition Reactions.- C. Diels-Alder Reactions.- 11.4 Preparation.- A. Direct Synthesis.- B. Catalytic Reactions of Disilanes.- C. Pyrolysis.- D. Hydrosilation Reactions.- E. Dissolving Metal Reductions.- F. Wittig Reactions.- G. Allylic Organometallics.- 11.5 Silyl Substituted Allylic Anions.- 11.6 Boron Substituted Allylic Silanes.- 12 Electrophilic Reactions of Silyl Enol Ethers.- 12.1 Introduction.- 12.2 Carbocations.- 12.3 ?-Methylene Ketones.- 12.4 Cationic Iron Tricarbonyl Complexes.- 12.5 Halogens.- 12.6 ?-Halo Acyl Silanes.- 12.7 Pseudo Halogens, Sulfenyl and Selenyl Halides.- 12.8 Nitrosonium and Nitronium Cations.- 12.9 Mercuric Salts.- 12.10 Acid Chlorides.- 12.11 Aldehydes and Ketones.- 12.12 Silyl-Reformatsky Reactions.- 12.13 Acetals and Ketals.- 12.14 ?,?-Unsaturated Ketones, Ketals and Acetals.- 12.15 ?-Nitro Alkenes.- 12.16 Relative Reactivities.- 12.17 Hydroboration.- 13 Oxidation of Silyl Enol Ethers.- 13.1 Introduction.- 13.2 Preparation of ?,?-Unsaturated Ketones.- 13.3 Preparation of 1,4-Diketones.- 13.4 Preparation of ?-Acyloxy and a-Hydroxy Ketones.- 13.5 Baeyer-Villiger Oxidation of ?-Trimethylsilyloxy Ketones.- 13.6 Ozonolysis of Silyl Enol Ethers.- 13.7 Reaction of Singlet Oxygen with Silyl Enol Ethers.- 14 Cyclopropanation of Silyl Enol Ethers, Chemistry of Trimethylsilyloxycyclopropanes.- 14.1 Introduction.- 14.2 Preparation of Trimethylsilyloxycyclopropanes. Regiospecific Conversion to Methyl Ketones.- 14.3 Acid Catalyzed Rearrangement of 1-Vinyl-1-trimethylsilyloxycyclopropanes.- 14.4 Pyrolysis of 1-Vinyl-1-trimethylsilyloxycyclopropanes.- 14.5 Reactions of Electrophiles with Trimethylsilyloxycyclopropanes.- 14.6 Reactions of Silyl Enol Ethers with Other Carbenes.- 15 Cycloaddition and Electrocyclic Reactions of Silyl Enol Ethers.- 15.1 Introduction.- 15.2 [2 + 2] Cycloaddition Reactions.- 15.3 Diels-Alder, [4 + 2] Cycloaddition Reactions.- 15.4 [3 + 4] and [3 + 2] Cycloaddition Reactions.- 15.5 Electrocyclic Reactions of Silyl Enol Ethers.- 16 Preparation of Silyl Enol Ethers.- 16.1 Introduction.- 16.2 Rearrangement of ?-Sily1 Ketones.- 16.3 Brook Rearrangement, ?-Silyl Ketones.- 16.4 Preparation of ?-Silyl Ketones.- 16.5 Conjugate Addition/Generation of Specific Lithium Enolates from Silyl Enol Ethers.- 16.6 Hydrosilation of Ketones.- 16.7 Silyl-Hydroformylation Reactions.- 16.8 1,4-Hydrosilation of ?,?-Unsaturated Carbonyl Compounds.- 16.9 Catalytic Isomerization of Allyloxyltrimethylsilanes.- 16.10 Dissolving Metal Reduction.- 16.11 Non-Nucleophilic Bases.- 16.12 TMS-Cl/Triethylamine/DMF and Related Systems.- 17 Ionic Hydrogenations.- 17.1 Introduction.- 17.2 Ionic Hydrogenation of Alkenes-Reduction of Carbocations.- 17.3 Stability of Functional Groups to Ionic Hydrogenation.- 17.4 Ionic Hydrogenation-Reduction of Non-Classic…