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sigma2

sigma2

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Published by: bhunkri on Apr 04, 2011
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04/04/2011

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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

4. Thus the ring opening of aziridine is a 4 electron process (=4n) with one antarafacial component. but only approximately. 3. This can also be (optionally) illustrated via the Frontier orbital approach.(conrotation) leaving one endocyclic and one exocyclic relative to the new ring. as for example. the lone pair counts as two electrons. The process in this case does not preserve an axis of symmetry exactly. the other from below (ie antarafacial). 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. a 4n reaction is predicted to proceed via a Hückel aromatic transition state with suprafacial bond formation and preserving a plane of symmetry. the HOMO of the butadiene fragment must rotate in the sense shown. In order to form a new sigma bond. Where heteroatoms are involved. Under photochemical conditions. and hence effectively the HOMO). one node coming from above the plane of the molecule. .

1002/anie. 6. 4n+2 (n=1) examples of steroidal reactions which could only be rationalised on the basis of the selection rules.196708701) for one resonance isomer .proceeding via a Möbius aromatic transition state with both methyl groups rotating in the same direction (conrotation) preserving an (approximate) axis of symmetry 5. One important aspect when counting electrons is to include only the cyclically conjugated system. In the example below (DOI: 10.

But. something else happens. the reaction proceeding suprafacially: . since they are apparently uninvolved in the reaction. From this mystery. science progressed (see blog entry). and the electrons in the central double bonds are NOT counted in the process. the arrow pushing gives rise to two independently cyclic six electron (4n+2) reactions. 7. if the [16] annulene is drawn in a different resonance form.of the [16] annulene shown. Carbanions contribute 2 electrons to the total count.

as a conundrum. go see the article here. 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. 9. . think about the following ring openings.1039/b510508k).8. 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. Finally. Recently. see DOI: 10.

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