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Hydrogenation and hydrogenolysis in synthetic organic chemistry

Paperback Engels 1977 9789029801010
Verwachte levertijd ongeveer 9 werkdagen

Samenvatting

Numerous examples are known of the application of catalyzed hydrogenation and hydrogenolysis reactions in synthetic organic chemistry. However, catalyst and reaction conditions are often chosen on the analogy of literature data without a good knowledge of the influence of reaction variables and of the structure of the reactant on the various possible modes of reaction. In order to improve such an intuitive procedure it is essential to dispose of an understanding of the reaction mechanisms which are operative in hydrogena­ tion and hydrogenolysis reactions and which govern i.a. the selectivity of a given pathway with respect to consecutive and parallel reactions. Although organic chemistry and, in particular, hydrogenation and hydro­ genolysis reactions remain an experimental science this book has been written to give the organic chemist the insight and know-how necessary to apply these reactions successfully to synthetic problems. I warmly recommend it as a book which will enable the organic chemist to rationalize many of the phenomena of catalytic hydrogenation and hydrogenolysis reactions, whereby it surely helps the organic chemist to solve forthcoming synthetic problems in this field. In addition, it seems to me a useful book for physical and physical-organic chemists working in the field of homogeneous and heterogeneous catalysis. Finally, the ten years' experience of both authors in the field of catalysis and synthetic organic chemistry - as reflected by some forty publications­ guarantees a well-considered review containing many examples directly from the bench.

Specificaties

ISBN13:9789029801010
Taal:Engels
Bindwijze:paperback
Aantal pagina's:168
Uitgever:Springer Netherlands
Druk:0

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Inhoudsopgave

I. Introduction.- 1. The reactions.- 2. The active site.- 3. Mechanistic investigations.- 4. The catalyst.- Heterogeneous catalysts.- Homogeneous catalysts.- Immobilized homogeneous catalysts.- 5. The metals.- 6. Reaction conditions.- Solvent.- Promotion and poisoning.- Pressure and temperature.- 7. Apparatus, procedures, and safety precautions.- II. Hydrogenation.- 1. Introduction.- Chemisorption.- Mechanism.- Kinetics.- Selectivity.- 2. Hydrogenation of alkenic double bonds.- Structure and reactivity.- Stereochemistry.- Isomerization.- Polyenes.- Unsaturated functional groups.- Hydrogenolizable groups.- 3. Hydrogenation of aromatic rings.- Partial Hydrogenation.- Stereochemistry.- Partial Hydrogenation of naphthalenes.- Reducible functions.- Side reactions.- 4. Semi-hydrogenation of carbon-carbon triple bonds.- The catalyst.- Monoynes.- Polyynes and enynes.- Functional groups.- 5. Hydrogenation of carbon-oxygen double bonds.- Aliphatic aldehydes and ketones.- Aromatic aldehydes and ketones.- Stereochemistry.- Selectivity.- Side reactions.- 6. Hydrogenation of carbon-nitrogen multiple bonds.- Nitriles.- Imines.- 7. Enantioselective Hydrogenation.- Catalysts.- Alkenes.- Ketones.- Imines.- III. Hydrogenolysis.- 1. Introduction.- Chemisorption.- Kinetics.- Selectivity.- Catalysts.- Mechanism.- 2. Carbon-hydrogen hydrogenolysis (exchange).- (sp3) carbon-hydrogen bonds.- (sp2) carbon-hydrogen bonds.- 3. Carbon-carbon hydrogenolysis.- Catalysts.- Mechanism.- Stereochemistry.- Regioselectivity.- Reactivity.- Selectivity.- 4. Carbon-oxygen hydrogenolysis.- (sp3) carbon-oxygen bonds.- alcohols and ethers.- acetals.- reductive alkylation of amines.- oxiranes.- Benzyl-oxygen bonds.- mechanism.- stereochemistry.- selectivity.- application.- (sp2) carbon-oxygen bonds.- vinyl-oxygen bonds.- aryl-oxygen bonds.- carboxylic acids, esters and anhydrides.- 5. Carbon-nitrogen hydrogenolysis.- Mechanism.- Stereochemistry.- Application.- 6. Carbon-sulphur hydrogenolysis.- Reactivity.- Stereochemistry.- Selectivity.- Application.- 7. Carbon-halogen hydrogenolysis.- Reactivity.- Stereochemistry and mechanism.- Selectivity.- Application.- 8. Hydrogenolysis of non-carbon bonds.- Nitrogen-oxygen bond.- Mechanism.- Reactivity.- Side reactions.- Selectivity.- Application.- Nitrogen-nitrogen bond.- Oxygen-oxygen bond.- Sulphur-oxygen bond.

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        Hydrogenation and hydrogenolysis in synthetic organic chemistry