In organic chemistry, keto–enol tautomerism refers to a chemical equilibrium between a keto form (a ketone or an aldehyde) and an enol (an alcohol). The enol and keto forms are said to be tautomers of each other. The interconversion of the two forms involves the movement of alpha hydrogen and the shifting of bonding electrons; hence, the isomerism qualifies as tautomerism.

A compound containing a carbonyl group (C=O) is normally in rapid equilibrium with an enol tautomer, which contains a pair of doubly bonded carbon atoms adjacent to a hydroxyl (−OH) group, C=C-OH. The keto form predominates at equilibrium for most ketones. Nonetheless, the enol form is important for some reactions. The deprotonated intermediate in the interconversion of the two forms, referred to as an enolate anion, is important in carbonyl chemistry, in large part because it is a strong nucleophile.

Normally, the keto–enol tautomerization chemical equilibrium is highly thermodynamically driven, and at room temperature the equilibrium heavily favors the formation of the keto form. A classic example for favoring the keto form can be seen in the equilibrium between vinyl alcohol and acetaldehyde (K = [enol]/ [keto] ≈ 3 × 10−7). However, it is reported that in the case of vinyl alcohol, formation of a stabilized enol form can be accomplished by controlling the water concentration in the system and utilizing the kinetic favorability of the deuterium produced kinetic isotope effect (kH+/kD+ = 4.75, kH2O/kD2O = 12). Deuterium stabilization can be accomplished through hydrolysis of a ketene precursor in the presence of a slight stoichiometric excess of heavy water (D2O). Studies show that the tautomerization process is significantly inhibited at ambient temperatures ( kt ≈ 10−6 M/s), and the half life of the enol form can easily be increased to t1/2 = 42 minutes for first order hydrolysis kinetics.

Mechanism. The acid catalyzed conversion of an enol to the keto form proceeds by a two step mechanism in an aqueous acidic solution. For this, it is necessary that the alpha carbon (the carbon closest to functional group) contains at least one hydrogen atom known as alpha hydrogen.This atom is removed from the alpha carbon and bonds to the oxygen of the carbonyl carbon to form the enol tautomer. The existence of hydrogen atom at alpha carbon is necessary but not sufficient condition for enolization to occur. To be acidic, the alpha hydrogen should be positioned such that may line up parallel with antibonding pi-orbital of the carbonyl group. The hyperconjugation of this bond with C–H bond at alpha carbon reduces the electron density out of C–H bond and weakens it. Thus the alpha hydrogen becomes acidic. When this requirement is not enforced, for example in the adamantanone or other polycyclic ketones, the enolization is impossible or very slow.

First, the exposed electrons of the C=C double bond of the enol are donated to a hydronium ion (H3O+). This addition follows Markovnikov's rule, thus the proton is added to the carbon with more hydrogens. This is a concerted step with the oxygen in the hydroxyl group donating electrons to produce the eventual carbonyl group.

One of the early investigators into keto–enol tautomerism was Emil Erlenmeyer. His Erlenmeyer rule, developed in 1880, states that all alcohols in which the hydroxyl group is attached directly to a double-bonded carbon atom become aldehydes or ketones. This conversion occurs because the keto form is, in general, more stable than its enol tautomer. The keto form is therefore favored at equilibrium because it is the lower energy form.

Keto–enol tautomerism is important in several areas of biochemistry. The high phosphate-transfer potential of phosphoenolpyruvate results from the fact that the phosphorylated compound is "trapped" in the less stable enol form, whereas after dephosphorylation it can assume the keto form. Rare enol tautomers of the bases guanine and thymine can lead to mutation because of their altered base-pairing properties.



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