Examples Of Electrocyclic Reactions.

1. Opening of the cyclopropyl cation involves only one electron arrow, and hence the
number of cyclically conjugated electrons is 2 (4n+2, n=0). Under thermal conditions,
this will go via a Hückel aromatic transition state involving a suprafacial component,
which has the effect of rotating both methyl groups outwards in opposite directions
(disrotation) and in the process preserving a plane of symmetry.

Note that in the transition state model, the leaving group (protonated water in this model)
has not entirely departed before the electrocyclic ring opening starts. In reality, the SN1
solvolysis and the electrocyclic pericyclic may in fact be synchronous with each other,
rather than comprising two separate and distinct steps (i.e. both steps together constitute a
single concerted process). This could be thought of as a solvolytically-assisted pericyclic
reaction.

2. Both the reactions below involve two electron arrows and hence are 4n systems (n=1).

Thermally, they will proceed via a Möbius aromatic transition state involving one
antarafacial component. Both methyl groups will rotate in the same direction
 (conrotation) leaving one endocyclic and one exocyclic relative to the new ring. The
process in this case does not preserve an axis of symmetry exactly, but only
approximately. This can also be (optionally) illustrated via the Frontier orbital approach.

In order to form a new sigma bond, the HOMO of the butadiene fragment must rotate in
the sense shown, one node coming from above the plane of the molecule, the other from
below (ie antarafacial).

3. Under photochemical conditions, a 4n reaction is predicted to proceed via a Hückel

aromatic transition state with suprafacial bond formation and preserving a plane of
symmetry, as for example;

The sense of this can again be seen from the frontier orbital (normally the LUMO but in
the excited state occupied by a single electron, and hence effectively the HOMO).

4. Where heteroatoms are involved, the lone pair counts as two electrons. Thus the ring
opening of aziridine is a 4 electron process (=4n) with one antarafacial component,
 proceeding via a Möbius aromatic transition state with both methyl groups rotating in
the same direction (conrotation) preserving an (approximate) axis of symmetry

5. 4n+2 (n=1) examples of steroidal reactions which could only be rationalised on the basis
of the selection rules;

6. One important aspect when counting electrons is to include only the cyclically conjugated
system. In the example below (DOI: 10.1002/anie.196708701) for one resonance isomer
 of the [16] annulene shown, the arrow pushing gives rise to two independently cyclic six
electron (4n+2) reactions, and the electrons in the central double bonds are NOT counted
in the process, since they are apparently uninvolved in the reaction;

But, if the [16] annulene is drawn in a different resonance form, something else happens.
From this mystery, science progressed (see blog entry).

7. Carbanions contribute 2 electrons to the total count, the reaction proceeding

suprafacially:
8. Recently, an example has been proposed which would demonstate a double-twist
Möbius transition state exhibiting two antarafacial components (a double "S" = "figure 8"
transition state is aromatic for 4n+2 electrons, see DOI: 10.1039/b510508k).

9. Finally, as a conundrum, think about the following ring openings, and whether they
proceed via a Hückel or a Möbius transition state?

Is this last example an electrocyclic reaction or a cycloelimination reaction? For an

analysis of this point, go see the article here.