CM3031 - Organic Reaction

Mechanism and Synthesis

MihaiELA C. Stuparu
Office: CBC 05-01
Email: mstuparu@ntu.edu.sg

Division of Chemistry and Biological Chemistry

School of Physical and Mathematical Sciences
Nanyang Technological University

S2-2019
1
 Pericyclic Reactions
Sigmatropic
Rearrangements/Reactions
!! cyclic transition structures
!! all bond-forming and bond-breaking takes place in concert-
without the formation of an intermediate

- unimolecular isomerization
- movement of a s bond from one position to another, with the movement of the conjugates
system to accommodate the new bond

[1,n] shifts [m,n] shifts (rearrangements)

S2-2019
2
[1,5] shifts

3
 [1,5] shifts

By [1,5]-shifts, not [1,7]

4
 [3,3]-SgmS-Stereochemistry

Johnson-Claisen
OH CH3C(OEt)3, cat. H+
CO2Et

H OH
OEt H+ OEt OEt
- EtOH
Me OEt Me OEt Me
OEt OEt OEt
H
EtO OEt EtO OEt OEt
H+ - EtOH H - H+
Me O Me O O

OEt OEt
O [3,3]-sigmatropic shift O

5
 [3,3]-SgmS-Stereochemistry

[3,3]-sigmatropic shift with nitrogen: aza-Claisen

Me Me
HO HO
AgNO3

N CN N
Me AgNO3 Me

HO Me O
Me

N N
H Me
Me

6
 [3,3]-SgmS-Stereochemistry

The Cope rearrangement -releases of ring strain allows reactions at lower temperatures

Ph3P=CH2
OHC
n-Bu n-Bu

7
 [2,3]-SgmS-Stereochemistry

Sommelet-Hauser: [2,3]-sigmatropic rearrangements of ylids

Me Me H2C Me NMe2 NMe2

N Me N Me
base Me

CO2Me CO2Me
Me Me
S S