These rearrangements all proceed via a species conrtaining
a three membered ring (readily formed under kinetic conditions,
as the entropic cost of forming such a ring is very low). These
rings are highly strained (as all the substituents are eclipsed)
so are then readily opened in the course of the rearrangement.
(This removal of ring strain may in some cases actually provide
the driving force for the rearrangement.)
Favorskii
The Favorskii is a useful reaction for ring contraction.
Payne Rearrangement
If a bulky nucleophile is present it will attack the less hindered
of the two epoxides. For example;
Entropically favoured
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Steps like the second step here which involve loss of a stable
gaseous molecule (N2 is possibly the best of all
as it is highly inert and has a lot of bond energy - this makes
compounds that are able to lose N2 rather explosive!)
are very favourable entropically (increase
of disorder!) and therefore not uncommon in rearrangements,
for hich they can provide the thermodynamic driving force. |
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