Chapter 19 reaction summary

Reaction Comments
O
O
NaOH Difficult to stop before
Aldol 2 H
H dehydration
OH
O
O
Aldol with NaOH
2 H
dehydration
H

O O
O The aldol acceptor cannot
Mixed aldol H + NaOH
have -hydrogens

O
1. NaOEt O O
Claisen 2
OEt 2. H 3O+
OEt
O O
OEt 1. NaOEt
Dieckmann EtO CO2Et Cyclic Claisen reaction
2. H 3O+
O
O O
1. NaOEt O O
+
Acylation of ketones
EtO OEt 2. H 3O+ OEt

O
N
Alkylation of 1. Br Better method to alkylate a
enamines ketone
2. H 3O+

O O
N O
Acylation of 1.
Cl
enamines
2. H 3O+

O O
O O Can hydrolyze ester to
Acetoacetic ester 1. NaOEt
OEt carboxylic acid then
synthesis OEt 2. Br decarboxylate
O O O O
Acetoacetic ester 1. NaOEt Can hydrolyze ester to
synthesis OEt OEt carboxylic acid then
2. Br
Dialkylation decarboxylate

O O
O O Can hydrolyze ester to
Malonic ester 1. NaOEt
EtO OEt carboxylic acid then
synthesis EtO OEt 2. Br decarboxylate
O O O O
Malonic ester 1. NaOEt Can hydrolyze ester to
synthesis EtO OEt EtO OEt carboxylic acid then
2. Br
Dialkylation decarboxylate

O CO2Et Stabilized carbanions add

1. NaOEt
+ EtO 2C CO2Et 1,4 to ,-unsaturated
Michael addition 2. H 3O+ EtO 2C carbonyl. Carbanion can be
O more than malonic ester
 Chapter 19 reaction summary

Reaction Comments
O
1. R 2CuLi R O Cuprates (unlike Grignards)
Cuprate addition add 1,4 to ,-unsaturated
2. H 3O+ carbonyl
O R O
1. R 2CuLi
Cuprate addition with 2. Br
Can couple cuprate 1,4-
-alkylation additon with alkylation