Recitation Chapter 19

ANNOTATED
Enolates and Enamines

Mar 10, 2016

Thurs. pm

DINE
Devise a synthetic scheme (no
restrictions):

DINE
Devise a synthetic scheme (no
restrictions):

1. LiAlH4,
THF
2. H+ or
H2O*

NaBH4,
EtOH

Zn(Hg),
HCl

H2NNH2, NaOH
Ethylene
glycol, H2O

H2, Pt/C

NO!
Too
reactive

1o OH

1o OH

1o OH

alkane
alkane + N2
methylen methylene
e

1o OH

2o OH

2o OH

alkane
alkane + N2
methylen methylene
e

2o OH

1o OH

NO!

NO!

1o OH

NO!

NO!

NO!

-NH2*

NO!

NO!

v. High
temp
and
pressure

no

Ideas for synthesis;

may see in box problems:

Recognize these in the

Products!

hydroxy aldehyde (Aldol)

hydroxy ketone (Aldol)
-keto acid (decarboxylation)
, unsat ketone (Michael acceptor)
1,5-dicarbonyls (Michael)
, unsat ketone in ring (Robinson)

Recognize these in the Products:

ALDOL

Beta hydroxy aldehyde (Aldol)

Beta hydroxy ketone (Aldol)
OR dehydrated versions: ,-unsat
carbonyl

Recognize these in the Products!

-OH

Recognize these in the Products:

Beta-keto Acid: WILL decarboxylate!

OR Can start as beta-keto

ester, then
1. NaOH, H2O
2. H+
3.

Recognize these in the Products!

1,5-dicarbonyls Came from
MICHAEL addition

3
1

NOTE: Only Grignards, Alkyl lithiums, and hydride

ADD 1,2!
All other nucs, add 1,4.
This IS a different 1-4 than the 1-5 above!!

Recognize these in the Products!

, unsat ketone in ring (Robinson)

NUMBER the 1-5 di-carbonyl from the
(original) Michael Addition!
1
5

2
3

Robinson Annulation

Enolate
vs
Enamine

Enolate

vs

Enamine

C alkylation (major)
O (minor)
Multi-alkylation
PRODUCT mixes
C alkylation
product

Enolate

vs

Enamine

PRODUCT mixes

C alkylation
There IS no O
Less reactive, not basic
Milder, not prone to multialkylation

Enamine: SO, recognize for box

problems

3
.

Extras

C-C bond, but nitrogen, too

Reduce to Amine*
then can make Amide; add acyl halide