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Organic Chemistry: Enamines & Reactions

The document summarizes key concepts in organic chemistry covered in lectures 38 and 39. It discusses enamines as specific enol equivalents that are good for condensations with aldehydes and ketones. It also describes how removing one product from carbonyl condensations allows control over the reaction. Lastly, it introduces 1,5-dicarbonyl compounds and explains how Robinson ring annulation combines aldol and Michael reactions.

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102 views9 pages

Organic Chemistry: Enamines & Reactions

The document summarizes key concepts in organic chemistry covered in lectures 38 and 39. It discusses enamines as specific enol equivalents that are good for condensations with aldehydes and ketones. It also describes how removing one product from carbonyl condensations allows control over the reaction. Lastly, it introduces 1,5-dicarbonyl compounds and explains how Robinson ring annulation combines aldol and Michael reactions.

Uploaded by

living luxurious
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PPTX, PDF, TXT or read online on Scribd
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CHEM F311 Organic Chemistry – III

Lecture 38 and 39 – 05th Dec. 2022


Recap
 Mannich reaction

 Use of specific enol equivalents

 Activating groups
 Wittig and Reformatsky reagents

Preview
 Enamines as specific enol equivalents

 Control in carbonyl condensations – through removal of one product

 1,5-Dicarbonyl compounds

 Robinson ring annulation / annelation


Enamines

The best specific enol equivalents for aldehydes is enamines; enamines


are also good for ketones.

R'CH 2CHO + R2NH ' NR2


R

E E E
H 2O
' NR2 '
NR2 '
O
R R H R

20 amines are generally used for enamine formation


O

N N N
H H H
O

Ar
CHO
O
H
N Ar
ArCOCl H2O
N TM
CHO H + N
80 % yield
Removal of one product [controlling carbonyl condensation]

O O OH
Ph O
PhCHO
base
Ph (not formed)

O O
O O O O
CH2O, K2CO3
CO2Et CO2Et O
O
OH
N PhCHO
H PhCHO HCl
HCl
O O
OH O O O O
HCl
HO O Ph Ph O
O
O
Ph O O

(Only product)
1,5-difunctionalised compounds, Michael addition & Robinson
Annelation (or Annulation) O
O
R1
O O R1
or +
+ O
R1 R2 O
R2
R2
Using activating groups
O

CO2H
Using enamine formation
O
CO2Me

Michael acceptors by the Mannich reaction


O
CO2Et

CO2Et
Robinson Annelation (combining Aldol and Michael reaction)
O
CO2Et

Ph Ph
O

O O

OH OH
OH (i) NaOH, H2O
CH2(COOEt)2
COOEt (ii) H+, H2O COOEt
base
CHO (iii) EtOH / H+
COOEt

Raney Ni, H2
O OH
CrO3
NaOEt
TM COOEt
COOEt AcOH

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