Preparative Polar Organometallic Chemistry

Sulfides and Alkyl Aryl Sulfides.- 2.6 Dialkyl and Alkyl Aryl Sulfoxides and Sulfones.- 3 Experiments.- 3.1 Lithiation of Formaldehyde Dimethylthioacetal with BuLi in THF and Hexane.- 3.2 Lithiation of Formaldehyde Dimethylthioacetal with BuLi · TMEDA in Hexane.- 3.3 Reaction of Lithiated Bis(methylthio)methane with Alkyl Halides.- 3.4 Hydroxyalkylation of Lithiated Bis(methylthio)methane with Epoxides.- 3.5 Reaction of Lithiated 1,3-Dithiane with 1-Bromo-3-chloropropane and Ring Closure of the Coupling Product Under the Influence of Butyllithium.- 3.6 Hydroxymethylation of Bis(methylthio)methane with Paraformaldehyde.- 3.7 Reaction of Lithiated Bis(methylthio)methane with Dimethylformamide and Subsequent Acid Hydrolysis.- 3.8 Reaction of Lithiated Bis(methylthio)methane with Carbon Dioxide.- 3.9 Reaction of Lithiated Bis(methylthio)methane with Dimethyl Disulfide and Trimethylchlorosilane.- 3.10 Lithiation of Methoxymethyl Phenyl Sulfide and Subsequent Reaction with Dimethylformamide.- 3.11 Reaction of Lithiated Bis(methylthio)methane with Methyl Isothiocyanate and N,N-Dimethyl Carbamoyl Chloride.- 3.12 Peterson Olefination Reactions with Lithiated Trimethylsilyl Bis(methylthio)methane. Preparation of Ketene Thioacetals.- 3.13 Conjugate Addition of Lithiated S,S-Acetals and Corresponding S-Oxides to 2-Cyclohexen-1-one and Methyl Acrylate.- 3.14 Lithiation of Dimethyl Sulfide and Methyl Phenyl Sulfide and Subsequent Reaction of the Lithium Compounds with Benzaldehyde and Trimethylchlorosilane.- 3.15 Lithiation of (Trimethylsilylmethyl)Phenyl Sulfide and Subsequent Reaction with Acetone.- 3.16 Dilithiation of Methyl Phenyl Sulfide and Subsequent Trimethylsilylation.- 3.17 Reaction of Bis(methylthio)methane with Potassium Amide in Liquid Ammonia and Subsequent Reaction with Oxirane..- 3.18 Reaction of Dimethylsulfoxide with Sodamide in Liquid Ammonia and Subsequent Alkylation with Bromohexane.- 3.19 Mono-Deuteration of Bis(ethylthio)methane.- 3.20 Lithiation of Methyl Phenyl Sulfoxide with LDA and Subsequent Alkylation with Butyl Bromide.- 3.21 Preparation of Formaldehyde-S,S-Acetals.- 3.22 Preparation of Ethylthiomethyl Ethyl Sulfoxide and Methyl Phenyl Sulfoxide.- 3.23 Preparation of Benzaldehyde Dimethylthioacetal.- 4 Selected Procedures from Literature.- IV. ?-Metallation of Derivatives of Toluene Containing Heterosubstituents.- 1 Scope of this Chapter.- 2 Experiments.- 2.1 Metallation of N,N-Dimethyl-ortho-Toluidine.- 2.2 Synthesis of ortho-Pentylphenol via Potassiation of O-Protected ortho-Cresol.- 2.3 Dimetallation of ortho-Cresol.- 2.4 Metallation of o-and p-Tolunitrile with Alkali Amides in Liquid Ammonia and Alkali Diisopropylamide in THF-Hexane Mixtures.- 2.5 ?-Lithiation of p-Toluene-N,N-Dimethylsulfonamide.- V. Metallation of Heterosubstituted Allylic and Benzylic Compounds.- 1 Introduction.- 2 Substrates and Metallation Conditions.- 2.1 Allylic Amines and Ethers.- 2.2 Allylic and Pentadienylic Sulfur, Silicon and Selenium Compounds.- 2.3 Benzylic Amines, Silanes and Sulfides.- 2.4 Regiochemistry of the Reactions of Allylic Alkali Metal Compounds with Electrophiles.- 3 Experiments.- 3.1 Metallation of N,N-Dialkyl Allylamines with BuLi · TMEDA and BuLi · t-BuOK.- 3.2 Metallation of Allyl t-Butyl Ether with BuLi · t-BuOK.- 3.3 Lithiation of Allyl Trimethylsilane with BuLi · TMEDA.- 3.4 Lithiation of Methyl Allyl Sulfide and Phenyl Allyl Sulfide with BuLi.- 3.5 Metallation of Methyl Isopropenyl Ether with BuLi · t-BuOK.- 3.6 ?-Metallation of Benzyl Dimethylamine with BuLi · t-BuOK.- 3.7 Lithiation of Methyl Benzyl Sulfide and Benzyl Trimethylsilane.- 3.8 Preparation of N,N-Dimethyl Allylamine and N,N-Diethyl Allylamine.- 3.9 Preparation of t-Butyl Allyl Ether.- 3.10 Methyl Allyl Sulfide, Methyl Benzyl Sulfide and Phenyl Allyl Sulfide.- 3.11 Preparation of Allyl Trimethylsilane.- VI. Metallation of Heterocyclic Compounds.- 1 Introduction.- 2 Metallation of Alkyl Derivatives of Pyridine and Quinoline.- 3 Lateral Metallation of 2-Substituted Oxazolines, Thiazolines, Dihydrooxazines and Thiazoles.- 4 Experiments.- 4.1 General Procedure for the Metallation of Mono-, Di- and Trimethyl Pyridines and Quinolines in Liquid Ammonia and the Subsequent Alkylation.- 4.2 Conversion of 2-Methylpyridine, 2,4-Dimethylpyridine, 2,6-Dimethylpyridine and 2,4,6-Trimethylpyridine into the 2-Lithiomethyl Derivatives.- 4.3 Regiospecific Generation of 4-Metallomethylpyridines in Organic Solvents.- 4.4 Metallation of 3-Methylpyridine.- 4.5 Lithiation of 2-Methylthiazoline.- 4.6 Lithiation of 2,4,4,6-Tetramethyl-5,6-dihydro-1,3-oxazine.- 4.7 Dimetallation of 2,6-Dimethylpyridine.- 5 Organic Syntheses Procedures.- VII. Metallation of Aldimines and Ketimines.- 1 Introduction.- 2 Conditions for the Metallation.- 3 Experiments.- 3.1 Lithiation of Aldimines and Ketimines with LDA.- 3.2 Alkylation of Lithiated Imines.- 3.3 Metallation of Aldimines by Sodamide in Liquid Ammonia.- 3.4 Trimethylsilylation and Methylthiolation of Lithiated Imines.- 3.5 Conversion of Imines into Aldehydes and Ketones.- 3.6 Synthesis of ?,?-Unsaturated Aldehydes from Trimethylsilylated Aldimines.- 3.7 Preparation of Aldimines and Ketimines.- 4 Organic Syntheses Procedures.- VIII. Metallation of Nitriles and Isonitriles.- 1 Introduction.- 2 ?-Metallation of Nitriles.- 3 Metallation of Isonitriles.- 4 Experiments.- 4.1 Metallation of Nitriles with Alkali Amide in Liquid Ammonia.- 4.2 Lithiation of Nitriles and Isonitriles in a Mixture of THF and Hexane.- 4.3 Alkylation of Metallated Nitriles in Liquid Ammonia and in Organic Solvents.- 4.4 Reaction of Metallated Nitriles with Aldehydes and Ketones.- 4.5 Reaction of Lithioacetonitrile with Epoxides.- 4.6 Reaction of Lithiomethyl Isocyanide with Hexyl Bromide, Oxirane and Cyclohexanone.- 4.7 Conversion of Acetaldehyde into the Cyanohydrine and Protection of the OH-Group of the Cyanohydrine with Ethyl Vinyl Ether.- IX. Generation of Lithium Halocarbenoids.- 1 Introduction.- 2 Methods of Generation of Lithium Halocarbenoids.- 3 Experimental Conditions and Techniques in Carbenoid Chemistry.- 4 Experiments.- 4.1 Lithiation of Dichloromethane.- 4.2 Lithiation of 1,1-Dichloroalkanes.- 4.3 Lithiation of Dibromomethane.- 4.4 Lithiation of Chloroform.- 4.5 Lithiation of Bromoform.- 4.6 Lithiation of 7,7-Dibromonorcarane.- 4.7 Lithiation of Ethyl Bromoacetate.- X. Metallation of Carbonyl and Thiocarbonyl Compounds.- 1 Introduction.- 2 Mono Metallation of Carbonyl and Thiocarbonyl Compounds.- 3 Other Methods for the Generation of Enolates and Enethiolates.- 4 Dimetallation of Carbonyl and Thiocarbonyl Compounds.- 5 Experiments.- 5.1 Conversions of Ketones into Lithium Enolates and Subsequent Trimethylsilylation (General Procedure).- 5.2 Reaction of 1-Trimethylsilyloxy-l-Heptene with Butyllithium.- 5.3 Metallation of Carboxylic Esters with LDA.- 5.4 Metallation of Carboxylic Esters with Alkali Amides in Liquid Ammonia.- 5.5 Metallation of N-Methylpyrrolidine and ?-Butyrolactone with LDA.- 5.6 Lithiation of Methyl Crotonate.- 5.7 Lithiation of Thiolesters, Thionesters and Dithioesters with LDA (General Procedure).- 5.8 Metallation of Dithioesters with Alkali Amides in Liquid Ammonia.- 5.9 Dimetallation of Carboxylic Acids.- 5.10 Dimetallation of Pentane-2,4-dione with Sodamide in Liquid Ammonia.- 5.11 Dimetallation of Pentane-2,4-dione with LDA.- 5.12 1-Trimethylsilyloxy-l -heptene.- Metallation-Functionalization Index (Vol. 2).- Syntheses of Reagents and Starting Compounds (Vols. 1 and 2)..- Complementary Index (Vols. 1 and 2).- Typical Procedures and Special Techniques (Vols. 1 and 2).- Purification and Storage and Some Reagents and Solvents (Vols. 1 and 2).