Beschreibung
Autorenporträt
Inhaltsangabe1 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.
