Answer:
Four common types of reactions involving carbonyl reactions: 1) nucleophilic addition; 2) nucleophilic acyl substitution; 3) alpha substitution; 4) carbonyl condensations. The first two were previously discussed and the second two involve the properties of the carbon directly adjacent to the carbonyls, α carbons.
Alpha-substitution reactions results in the replacement of an H attached to the alpha carbon with an electrophile.
The nucleophile in these reactions are new and called enols and enolates.
Explanation:
The carbon in the carbonyl is the reference point and the alpha carbon is adjacent to the carbonyl carbon.
Hydrogen atoms attached the these carbons denoted with Greek letters will have the same designation, so an alpha hydrogen is attached to an alpha carbon.
Aldehyde hydrogens not given Greek leters.
α hydrogens display unusual acidity, due to the resonance stabilization of the carbanion conjugate base, called an enolate.
Tautomers are readily interconverted constitutional isomers, usually distinguished by a different location for an atom or a group, which is different than resonance.
The tautomerization in this chapter focuses on the carbonyl group with alpha hydrogen, which undergo keto-enol tautomerism.
Keto refers to the tautomer containing the carbonyl while enol implies a double bond and a hydroxyl group present in the tautomer.
The keto-enol tautomerization equilibrium is dependent on stabilization factors of both the keto tautomer and the enol tautomer, though the keto form is typically favored for simple carbonyl compounds.
The 1,3 arrangement of two carbonyl groups can work synergistically to stabilize the enol tautomer, increasing the amount present at equilibrium.
The positioning of the carbonyl groups in the 1,3 arrangement allows for the formation of a stabilizing intramolecular hydrogen bond between the hydroxyl group of the enol and the carbonyl oxygen as well as the alkene group of the enol tautomer is also conjugated with the carbonyl double bond which provides additional stabilization.
Aromaticity can also stabilize the enol tautomer over the keto tautomer.
Under neutral conditions, the tautomerization is slow, but both acid and base catalysts can be utilized to speed the reaction up.
Biological enol forming reactions use isomerase enzymes to catalyze the shifting of a carbonyl group in sugar molecules, often converting between a ketose and an aldose in a process called carbonyl isomerization.
