chapter 22. the chemistry of enolate ions, enols, and αβ ... materials... · chapter 22. the...
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Chapter 22. The Chemistry of Enolate Ions, Enols, and α,β-Unsaturated Carbonyl
Compounds
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Acidity of carbonyl compounds
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An orbital interaction of acetaldehyde
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Acid- or base-catalyzed enolization
Base-catalyzed
Acid-catalyzed
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Racemization through enolization Acid-catalyzed
Base-catalyzed
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For comparison: Br2 addition to alkenes
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Haloform Reactions
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Prepare α,β-unsaturated carbonyl compounds using aldol condensation
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Claisen Condensation
Rainer Ludwig Claisen
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Dieckmann condensation: intramolecular Claisen condensation
Walter Dieckmann
University of Munich
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Crossed Claisen condensation
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Conjugate addition reactions with ester and nitrile
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Acid-catalyzed conjugate addition reactions
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1,2- vs 1,4-additionWith 1,3-butadiene
With α,β-unsaturated carbonyl compounds
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Comparison between conjugate addition and carbonyl addition
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Thermodynamic control vs. kinetic control products
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Robinson Annulation
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Reduction with LAH is kinetically controlled