1. Synthesis of Ketones From Acids
Dry
THF
RCOOH
LiOH
RCOO- Li+ +
Dry
THF
RCOO- Li+
+ R’- Li+
DIANION
IMPORTANT: NO WATER TO HERE
HOH H+
GEM DIOL

2. Example of Ketone from Acid

3. Synthesis Using Acid and RLi
Convert PhEt to Cyclopropyl ethyl ketone
LiOH
2. EtLi
3. HOH H+
How could one prepared benzoic acid
From ethyl benzene?
Side-chain oxidation!!!!
Appears as if we could start with benzoic acid and introduce ethyl group by EtLi.

4. Synthesis of Aldehydes and Ketones from Acid Chlorides
1. Preparation of acid chlorides
R = almost anything!! H, Alkyl, Aryl, etc
2. Preparation of aldehydes - bulky reducing reagents
Reduction to ROH does not occur - steric -

5. Synthesis of Ketones
Recall that ketones react with acid chlorides to give alcohols.
TO STOP AT KETONE STAGE, NEED A MILDER ORGANOLITHIUM

6. USE OF ORGANO CUPRATES Rli + CuI --------> R2CuLi
STOPS: addition to acid
chloride is much faster
than addition to ketone.

7. Example

8. Reactions of Carbonyls
Nucleophilic addition - pages
Base-promoted additions
Nucleophilic anion attacks C=O to give alkoxide
which is neutralized to alcohol by acidic work-up.
Acid-catalyzed additions
increases electrophilicity of carbonyl group
Relative rate of addition:
HCHO > RCHO> RCOR

9. WITTIG REACTION
+ Ph3P-O