1

Copyright 2012
James Ashenhurst
masterorganicchemistry.com

RMgX

OH

Aldehyde

OH

2 alcohol

OH
OR

Aldol Reaction

OH

NR2

OH

Cl

Acyl chloride

R'

R'

Ketone

R'

NR2

O
OR

OH

3 alcohol

O
R

OH
OR

R'

Aldol Reaction

NR2

OH

O
R

R'

RO

NR2

N
R

O
R
, unsaturated
ketone (enone)

Varies with
conditions: 1,2
adduct is
kinetic pdt.

Ester

O
OR

Michael Reaction

OH
OR

O
R

NR2

O
OR

3 alcohol

keto ester:
Claisen Condensation

Deprotonation

Deprotonation

Acid nitrile

NH2

Deprotonation

1 and 2 amides:
deprotonation
3amides: NR

Acetal

CN

Acid nitrile

Borderline

OR

HO

OH

R'

R'

Acetal
Requires acid
catalysis

1,3 diketone:
Claisen Condensation

Deprotonation

NR

Deprotonation

1 and 2 amides:
deprotonation
3amides: NR

NR

NR

O
R

Mix of addition
/deprotonation

NR2

O
OR

Borderline

R'

2 alcohol

NHR

CN

H
H

OH
R

R'

2 alcohol

O
OR'

OR'

Borderline reaction:
requires strong acid,
alcohol as solvent, heat

O
R

Varies with conditions: 1,2

adduct is kinetic product, 1,4
adduct is thermodynamic.

OH
OH

NR

OR

H
H
1 alcohol
R

O
R

H
H

OH
NR

1 alcohol

OH

NR

Amide Hydrolysis
Requires strong
conc. acid, heat
R

H
H
2 alcohol

OH

Fischer esterification
(requires acid, heat)

NR

OH
R

Note: Easily
reversible

NR

NHR

1 alcohol

1 alcohol

Transesterification
Saponification
Can be done under basic (basic conditions)
or acidic conditions.
Can also hydrolyze
with aqueous acid
O

NR

RO

H
2 alcohol

RO

Amide

Amide

O
R

RO

NR

1 alcohol

Hydrate
see above: even less
favored than with aldehydes
due to sterics

O
R

NHR

Carboxylic Acid

Note: in both cases, very prone to

the reverse reaction (elimination)

Borderline

OH

OH
OH

RO

NC

OH

O
R

Ester

O
R

OH

Carboxylic acid

OR

LiAlH4
Lithium aluminum
hydride

OH

Ester

NaBH4

O
OR

11

Sodium
borohydride

Hydrate
(usu. thermodynaically
disfavored, except for
electron poor aldehydes)
If aldehyde is enolizable,
hydroxide can form enolate.

Usually requires
dehydration
agent (e.g. DCC)

O
R

OH

RHN

Carboxylic acid

CN

O
OH

OH

R
CN
R'
Cyanohydrin

HO

OR

Requires acid
catalysis to form

Michael Reaction

OH

RO

O
R

RO

Imine
(ketimine)

Note: best when ketones are

identical or when only one can
enolize (to avoid scrambling)

Cyanohydrin

10

H2O/
MOH
water/
hydroxide

O
NHR

Amide

OR

CN

O
R

ROH/
ROM
alcohol/
alkoxide

O
NHR

Amide
(Schotten-Bauman
reaction)

RO

Aldol Reaction

OH
R

R
O

Cyanide

Imine
(aldimine)

OH

RO

OH

R
R
R
3 alcohol

O
OR

MCN

N
R

Knoevenagel
Condensation

keto ester

OH

Anhydride

R
3 alcohol

O
O

RNH2
amine
(primary amine)

Aldol Reaction

RO

heating under basic conditions will lead to

elimination of OH - Aldol condensation
also note that reaction can be reversible
under basic conditions : Retro-aldol reaction

6
M

keto ester
enolate

Enamine

RO

5
O

NR2

R
Ketone enolate

4
M

OR
Ester enolate

Grignard

3
M

OH

NR

NH2
H
Amine

R
Alkyl halide

Enolate
Alkylation

Enolate
Alkylation

Amine

Stork enamine
reaction
note: capable of
alkylating
a second time

caution! product
is a good nucleophile;
can obtain multiple
alkylations

Williamson
Ether Synthesis
requires basic
conditions

requires
basic
conditions

Alkane