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Ambident Nucleophiles The enolate is an ambident anion with the negative charge delocalized between the oxygen and carbon atoms. A major percentage of the charge is believed to be accomodated by the more electronegative oxygen atom; that is, structure ‘B’ makes a greater contribution to the resonance hybrid than does structure ‘A’. Electrons are held less tightly by the less electronegative carbon atom, thus the carbon atom is more polarizable than the oxygen. The electrons can be more easily shared with another atom during the bond-forming process of nucleophilic substitution. Solvation of the enolate anion, particularly in the common protic solvents, is another factor that favors reaction at carbon. The more-concentrated charge on oxygen results in greater solvation than that at the carbon atom. The more-solvated oxygen atom will be less available as a nucleophile. * Carbanions and Other Nucleophilic Carbon Species Many of the important reactions of aldehydes, ketones and members of the carboxylic acid family involve nucleophilic reactivity at the carbon atom alpha to the carbonyl group. It is possible for many compounds containing a carbonyl group to function either as electrphiles at the carbonyl carbon or as nucleophiles at the α-carbon atom. Nucleophilic reactivity can be attributed to properties imparted to the α-carbon atom by the adjacent carbonyl group. Enols and Enolate Anions Enolization of Aldehydes and Ketones The process whereby a hydrogen atom attached to the α-carbon atom of a carbonyl compound (the α-hydrogen atom) moves to the carbonyl oxygen atom is known as enolization or keto-enol tautomerism. Isomeric carbonyl and enol structures are tautomers. The enolization reaction rapidly reaches a state of equilibrium, the position of which is indicated by the equilibrium constant for tautomerism, KT. Normally, the carbonyl form is favored but structural factors markedly affect KT. 1,3-Dicarbonyl compounds for example, contain a relativel