CHEM F311 Organic Chemistry – III

Lecture 35 – 22nd Nov. 2022

Recap

 Diels Alder reaction

Stereospecificity, Stereoselectivity and Regioselectivity aspects

Preview

 Synthesis of carbonyl compounds – carbonyl condensation

 1,3-Dicarbonyl compounds

 β – hydroxyl carbonyl compounds

 Synthesis of α, β – unsaturated carbonyl compounds

 Carbonyl condensation
OAc
OH

OH NH2
O O
All the compounds have 1,3 relationship and can be made from
alcohol, ketone(or aldehyde) and carboxylic acid derivatives

Synthesis of difunctionalised compounds with odd numbered relationships

need only synthons of natural polarity; while opposite is true for
difunctionalised compounds with even numbered relationships.
 Two-group disconnections: 1,3-difunctional compounds & α,β-
unsaturated carbonyl compounds
O O

O OH Understanding 1,3-relationship

1,3-Dicarbonyl compounds
O O

OEt

Route (a) is preferred as it is self condensation of the molecule (ethyl acetate)

 O
O

O O O
COOEt O
base TM
+
O COOEt COOEt

CO2Et

O
O

N
β-hydroxy carbonyl compounds
O OH

OH

OH

O
Ph
α,β-unsaturated carbonyl compounds
Obtained from dehydration of β-hydroxy carbonyl compounds
OH O acid O
or base
O
O O
O
base
O TM

Ph
CHO
NaOH
3PhCHO + TM (80 % yield)
CHO H2O, EtOH
O

CONH2

CHO base
Ag2O 1.SOCl2 m-CPBA
TM
CONH2
COOH 2.NH3
CHO