Chem 212

Enolate Problem Set ANSWERS

Provide the products for the following reactions. O O

MeO OMe
O O O
O 1) NaOMe
1) LDA
*
MeO OMe 2) Br no asymmetric carbons
2) Br
racemic

O
O O O O 1) NaOMe
1) LDA HO
MeO OMe 2) Br no asymmetric carbons
2)
Br 3) H3O+, heat
racemic O O
O O O 1) NaOEt racemic
* OEt
1) Me2CuLi O
OEt 2) Br
2) H3O+ racemic

O no
O O O 1) NaOEt asymmetric
1) Et MgBr OH carbons
OEt 2) Br
2) H3O+ racemic
3) H3O+, heat
O
O O O O 1) NaOEt OH
1) LDA
O H EtO OEt Br no O
2) 2)
MeO asymmetric
Br O MeO carbons
3) H3O+, heat
3) H3O+
O O 1) NaOEt
O O
O * racemic
OEt 2) Et Br
1) LDA * O
O racemic 3) NaOEt
4) Br
2) Br
5) H3O+, heat

O O O O
O O
1) NaOEt O O 1) NaOEt no
asymmetric
* racemic 2) Br carbons
2) MeI
racemic

O O
O O
single no
NaH enantiomer 1) NaOMe asymmetric
carbons
OTs 2) O
O Br

5-membered rings form faster than 7-membered ones

MeO *
MeO
O 1) KOtBu H
1) LDA H
O
OtBu O 2) MeI H
2) CO O H O
O 3) KOtBu
Br 4) O
single enantiomer O I mixture of diastereomers

CO2Me 1) 1,2-ethanediol, H+
2) NH3, H2O, heat HN
* O O
3) LiAlH4 *
HO2C CHO 1) NaBH4, MeOH
4) excess H3O+ (2 steps in one) single
5) (conjugate addition!) O N enantiomer
O 2) Ac2O, pyridine N
1) form ketal mixed diastereomers
2) ester to amide 1) reduce aldehyde (only!) to primary alcohol
3) reduce amide to primary amine 2) form anhydride from alcohol which reacts
4) neutralize LiAlH4 reaction AND cleave ketal with carboxylic acid to form lactone
5) amine does conjugate acid addition