Keywords to grasp : enols, enolates and tautomerism
 

Trying to put it as simply as possible, enols are compounds that have alcohol groups, -OH, substituted directly onto alkenes, C=C, hence "alkene-ols" or enols. Enols can be viewed a alkenes with a strong electron donating substituent. Since alkenes themselves (review) typically react as nucleophiles, the -OH group makes them even more reactive than a simple alkene.
Enolates are the conjugate bases or anions of enols (like alkoxides are the anions of alcohols) and can be prepared using a base.

CHIME images of a ketone and the corresponding enol and enolate are shown below for comparison:
 

Question:
Both enols and enolates are potential nucleophiles, but enolates are better nucleophiles than enols.... Why ?
 

Acetone electrostatic potential

When comparing the two electrostatic potentials note the increased electron density on both the O (it's more red) and the C (less blue) in the enolate compared to the ketone.  (The more red an area is, the higher the electron density and the more blue an area is, the lower the electron density)

Acetone enolate electrostatic potential

 
 

In general enols are unstable compounds and they are in an equilibrium with a more favorable carbonyl group. This process is known as tautomerism and is catalyzed by both acids and bases.  Try to draw the mechanism for these processes before you look at the answers.  In the example shown, 2-propanone ( = acetone) and 2-propenol can be described as tautomers. This is really a specific type of constitutional isomerism.  If you look at the bond strengths of the C=C and O-H compared to C=O and C-H, you should be able to verify the greater stability of the carbonyl group.

However, some enols are reasonably stable (usually there is an extra stabilizing effect): for example phenols and 1,3-dicarbonyl compound

Enolates are in principle, capable of reacting as nucleophiles at either the C atom or at the O atom (see below).  This is shown by the drawing out the main two resonance contributors, see right.

Question:
Which of these two would you rank as being the more important contributor ? 

In fact, most of the reactions we will cover are reactions of the carbanion contributor !
This shows the merit of considering "minor" resonance contributors since they can be the ones controlling reactivity.

Question:
Which is the best nucleophile, a negatively charged C or a negatively charged O ?

Mechanism of Tautomerisation

• Tautomerisation is both acid and base catalyzed.
• The mechanisms of these process are shown below for propanone.
• In each case note that it is catalytic since the acid or the base is regenerated.

MECHANISM OF ACID CATALYZEDTAUTOMERISATION Step 1: First, an acid-base reaction. The Lewis basic O atom of the carbonyl is protonated by the acid catalyst giving an oxonium ion. Step 2: Another acid-base reaction.  Removal of an a-hydrogen by a water molecule functioning as a base allows formation of the C=C and neutralizes the positive charge on the O giving the enol and regenerates the catalyst. MECHANISM OF BASE CATALYZED TAUTOMERISATION Step 1: First, an acid-base reaction. Hydroxide functions as a base and removes the acidic a-hydrogen giving the reactive enolate. Step 2: The negative charge is resonance stabilized to the more electronegative O atom. Step 3: An acid-base reaction. The alkoxide deprotonates a water molecule reforming the catalyst hydroxide and the enol