Sigmatropic Rearrangement:

Sigmatropic rearrangement involves the migration of a σ bond that is flanked by one or more
conjugated systems to a new position within the system. The reaction is termed [i,j] sigmatropic
shift when the bond migrates from position [1,1] to position [i,j]. For example, a carbon-
hydrogen bond may move across a diene. It is an example of [1.5] sigmatropic rearrangement.

Characteristics of Sigmatropic Rearrangements

 The number of π-bonds and sigma bonds remains constant.

 Only heat and light are necessary for the reaction.

 Only relocation of the sigma bond occurs.

 Requires a conjugated system for the rearrangement.

Suprafacial and Antarafacial Shifts

All sigmatropic shifts can occur with either retention or inversion of the geometry of migrating group.In
cases of stereochemical retention the migrating group translates without rotation into the bonding
position, while in the case of stereochemic the migrating group both rotates and translates to reach its
bonded conformation

Sigmatropic shift with retention in stereochemistry

Sigmatropic shift with retention in stereochemistry

Sigmatropic shift with inversion in stereochemistry

[1,3] Sigmatropic Shift

It is a type of sigmatropic rearrangement in which migration of sigma bonds adjace to one or more π
systems to a new position in a molecule..

[1,3] Sigmatropic H-Shift

When [1,3] sigmatropic rearrangement takes place, the H-atom of the reactant is shift from the first
position to the third position to form products. The molecular formula the substance remains the same
during this rearrangement.

[1,3] Sigmatropic Hydrogen Shift Suprafacial and Antarafacial

 Describes the possibility of both suprafacial and antarafacial shifts in [1,3] sigmatropic
rearrangements.
[1,3] Sigmatropic Carbon Shift

When [1,3] sigmatropic rearrangement takes place, the carbon atom of the reactant is shifted
from the first position to third position to form products. The molecular formula f the substance
 remains the same during this rearrangement.

[1,5] Sigmatropic Shift

The [1.5] suprafacial shift is symmetry allowed and geometrically feasible When[1,5]sigmatropic
rearrangement takes place, the H-atom of reactant first position to the fifth position to form products.
[1,7] Sigmatropic shift

When [1.7] sigmatropic rearrangement takes place, the H-atom of the reactant is shifto from the first
position to the seven-position to form product. It involves an antarafaci component if carried out
thermally. [1,7] H-shift cannot occur antarafacially becam the molecule is a rigid ring, but that can occur
photochemically.
[ 1,7 ] shift of carbon take place in a similar manner.

Synthetic Applications:

An antarafacial [1,7] shift is observed in the conversion of lumisterol to vitamin D, where following an
electrocyclic ring-opening to previtamin D₂, a methyl hydrogen shifts. A [1,7]- H Shift occurs in the final
stages of the human body's synthesis of vitamin D from cholesterol. Here is the last step of
the Biosynthesis