Preparative Polar Organometallic Chemistry: Volume 2

ISBN-13: 9783540527497 / Angielski / Miękka / 1991 / 230 str.

Lambert Brandsma

Opis

Preparative Polar Organometallic Chemistry is a collection of laboratory procedures for the synthesis and functionalization of organoalkali and Grignard compounds. The second volume with methods for generation and transformation of compounds bearing the metal at an sp3 carbon complements the first in which the metal was bound to an sp2 carbon atom in the reagent. Synthetically important intermediates such as metallated S, S-acetales, imines, nitriles, isonitriles and ketones are illustrated. All procedures have been worked out in full detail and tested in the author's own laboratory. Both books are intended to be practical bench-top laboratory manuals for working organic chemists, from the student to the advanced scientist.

Spis treści

I. Reactivity of Polar Organometallic Intermediates.- 1 Introduction.- 2 Alkylation.- 2.1 Reactivity—A Qualitative Comparison of the Polar Organometallics.- 2.2 Scope of the Alkylation Reaction.- 2.3 Dialkylation.- 2.4 Remarks on the Reaction Conditions of Alkylations.- 3 Hydroxyalkylation with Epoxides.- 4 Hydroxyalkylation with Carbonyl Compounds.- 5 Formylation with Dimethylformamide.- 6 Carboxylation.- 7 Reaction of Organoalkali Compounds with Carbon Disulfide.- 8 Addition of Organoalkali Compounds to Isocyanates and Isothiocyanates.- 9 Sulfenylation.- 10 Trimethylsilylation.- 11 Reactions of Organometallic Compounds with Chloroformates and Dimethylcarbamoyl Chloride.- 12 Reactions of Organoalkali Compounds with Halogenating Agents.- 13 Conjugate Additions.- II. Metallation of Aromatic and Olefinic Hydrocarbons.- 1 Introduction.- 2 Metallation of Alkylbenzenes and Alkylnaphthalenes.- 3 Dimetallation of Aromatic Compounds.- 4 Metallation of Olefinic Compounds.- 5 Stereochemistry of Allylic Metallations.- 6 Dimetallation of Olefins.- 7 Experiments.- 7.1 Metallation of Toluene with BuLi · t-BuOK in Hexane.- 7.2 Metallation of 1- and 2-Methylnaphthalene with BuLi · t-BuOK.TMEDA in Hexane.- 7.3 ?-Metallation of Ethylbenzene.- 7.4 ?,??-Dimetallation of m-Xylene.- 7.5 Lithiation of Toluene, Xylene, Mesitylene with BuLi · TMEDA..- 7.6 Metallation of Propene and Isobutene.- 7.7 Metallation of Various Olefins with Strongly Basic Reagents.- 7.8 Metallation of Cyclohexene.- 7.9 Dimetallation of Isobutene.- 7.10 Metallation of Isoprene.- 7.11 Metallation of ?-Methylstyrene.- 7.12 Metallation of Indene.- 7.13 Metallation of Cyclopentadiene.- 7.14 Preparation of 1,4-Cyclohexadiene.- 7.15 Allylbenzene.- 8 Selected Procedures from Literature.- III. Metallation of Saturated Sulfur Compounds.- 1 Introduction.- 2 Substrates and Metallation Conditions.- 2.1 S,S-Acetals.- 2.2 Methoxymethyl Phenyl Sulfide.- 2.3 Ethythiomethyl Ethyl Sulfoxide.- 2.4 Orthothioformates.- 2.5 Dialkyl 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).