Now we're going to focus on one of the most important intermediates for all of organic chemistry, and that's called the enolate. Specifically, in the base catalyzed tautomerization mechanism, the base catalyzed version, we form a resonance-stabilized intermediate called an enolate. Let me show you. Remember that in the base catalyzed version, what winds up happening is that my O negative grabs the alpha proton right away. I wind up forming a double bond here and then kicking electrons up to the O. This gives me a possible resonance structure though where, on the one hand, I have the negative charge on the O, but I could easily resonate that down to the carbon. Then, it could resonate back up. Both of these are considered the enolate anion, and both of them are correct. But for the purposes of this section, one of these is going to be far superior in helping us predict what a product will look like. The one that we're going to use is the one where the negative charge rests on the carbon. Why? Because that's going to help us realize that alpha carbons in basic solution are actually good nucleophiles. That's totally different from anything else we've done with carbonyls before. Because up until this point, we've been taking carbonyls and we've been saying that they're good electrophiles, that it's good to add stuff here. But now what I'm telling you is that the alpha carbon is actually a good nucleophile, meaning that the alpha carbon can actually do this. Crazy. We have a whole new set of reactions. A whole new branch of carbonyl chemistry opens up to us when we use enolates. Now, what I want to do is I want to use the next section to compare nucleophilic addition, which is a mechanism we should already be familiar with the mechanism of enolates.
Enolate - Video Tutorials & Practice Problems
Formation of Enolates
Video transcript
General Reactions
Video transcript
By now, I really hope that you're familiar with nucleophilic addition because it's just that important. Remember that you've got a partially positive carbon on the carbonyl. Nucleophiles can attack it, kick electrons up to the O. I wind up getting a tetrahedral intermediate. Remember that at this point, that O negative has no other choice other than to protonate because it has no good leaving groups that it can kick out. It's just going to protonate instead and make a substituted alcohol. This is the reaction that Grignards undergo, that reduction undergoes, and lots of other negatively charged nucleophiles. But what happens if instead of reacting my carbonyl with any random nucleophile, what if I react it with a base, with a base specifically suited to take off an alpha proton? What's going to happen is that you've got an H. If you use a base to pull off a proton, what you're going to do is you're going to make an enolate anion. This is a completely new reactive species because now if I have a negative charge on that carbon, I can use it to attack random electrophiles. If I can attack electrophiles with my alpha carbon, that means that I'm going to have a way to put things on the alpha carbon, meaning that the products of these enolate mediated reactions are alpha-substituted carbonyls. We actually get things on the alpha carbon, and that's super important. Nucleophilic addition is what we're used to seeing with carbonyls. But the new mechanism that we're going to be using in this section are nucleophiles. You're now going to be substituting nucleophiles. You're now going to be substituting things on the alpha position. Notice that at the beginning, I had an H and I ended up with an E. That's going to be the whole theme of this area. When we deal with enolates, we're going to be using them to substitute hydrogens for whatever electrophiles we want to react with. I hope that made sense. That's the general reaction. Now let's move on to some specific reactions.
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