Nucleophilic Addition

carbonyl + H+ ————>

enol formation

which group is more reactive, enol or enolate?

the enolate is more reactive because they have negative charges

which hydrogen will get deprotonated on an asymmetric molecule?

the alpha hydrogen on the more-substituted carbon

how can you deprotonate the alpha hydrogen of the less substituted carbon?

use a bulks base (LDA) at low temperature

How many hydrogens can LDA remove?

1

carbonyl (with alpha hydrogens) + base + X2 ————>

halogenated carbonyl compound (all alpha-Hs replaced with X)

carbonyl (with alpha hydrogens) + acid + X2 ————>

halogenated carbonyl compound (only 1 alpha-H is replaced)

ketone + OH-, xs X2, H3O+ ————>

Carboxylate

aldehyde + OH- + acid/base ————>

aldol condensation

ester + RO- + H+ ————>

Beta-keto ester (claisen condensation)

what is the rule for claisen condensation?

The OR- group must watch the ester

Beta-keto ester + OH- + heat ———>

ketone (beta decarboxylation)

acetoacetic ester + ————>

1. RO-

2. R1Br

3. RO_

4. R2Br

5. H3O, heat

di-alpha-alkylated ketone

acetoacetic ester + ————>

1. RO-

2. R1Br

3. H3O, heat

di-alpha-alkylated ketone

malonic ester + ————>

1. RO-

2. R1Br

3. RO_

4. R2Br

5. H3O, heat

di-alpha alkylated carboxylic acid

malonic ester + ————>

1. RO-

2. R1Br

3. H3O, heat

di-alpha alkylated carboxylic acid