This is an interesting result I got when studying the [1,4] sigmatropic rearrangement of heptamethylbicyclo-[3.1.0]hexenyl cations. It fits into the last lecture of a series on pericyclic mechanisms, and just before the first lecture on conformational analysis. This is how they join.

The benzidine rearrangement is claimed to be an example of the quite rare [5,5] sigmatropic migration[cite]10.1021/ja00335a035[/cite], which is a ten-electron homologation of the very common [3,3] sigmatropic reaction ( e.g. the Cope or Claisen). Some benzidine rearrangements are indeed thought to go through the [3,3] route[cite]10.1021/ja00309a041[/cite]. The topic has been reviewed here[cite]10.1002/poc.610020702[/cite]. In

I have written earlier about dihydrocostunolide, and how in 1963 Corey missed spotting the electronic origins of a key step in its synthesis.[cite]10.1021/ja00952a037[/cite]. A nice juxtaposition to this failed opportunity relates to Woodward’s project at around the same time to synthesize vitamin B12. The step in the synthesis that caused him to ponder is shown below.

A dichotomy is a division into two mutually exclusive, opposed, or contradictory groups. Consider the reaction below*.* The bicyclic pentadiene on the left could in principle open on heating to give the monocyclic [12]-annulene (blue or red) via what is called an electrocyclic reaction as either a six (red) or eight (blue) electron process. These two possibilities represent our dichotomy;

I was intrigued by one aspect of the calculated transition state for di-imide reduction of an alkene; the calculated NMR shieldings indicated an diatropic ring current at the centre of the ring, but very deshielded shifts for the hydrogen atoms being transferred. This indicated, like most thermal pericyclic reactions, an aromatic transition state. Well, one game one can play with this sort of reaction is to add a double bond.

Not a few posts on this blog dissect the mechanisms of well known text-book reactions. But one reaction type where there are few examples on these pages are reductions. These come in three types; using electrons, using a hydride anion and using di-hydrogen. Here I first take a closer look at the third type, and in particular di-hydrogen as delivered from di-imide.

Semibullvalene is a molecule which undergoes a facile [3,3] sigmatropic shift. So facile that it appears this equilibrium can be frozen out at the transition state if suitable substituents are used. This is a six-electron process, which leads to one of those homologous questions; what happens with ten electrons? A 5,5 double Möbius sigmatropic rearrangement. Click for 3D model.

The four-electron thermal cycloaddition (in reverse a cheletropic elimination) of dichlorocarbene to ethene is a classic example of a forbidden pericyclic process taking a roundabout route to avoid directly violating the Woodward-Hoffmann rules.

I am following up on one unfinished thread in my previous post; a candidate was proposed in which the transition state for [3,3] sigmatropic rearrangement in a semibullvalene might be frozen out to become instead a stable minimum. The hypothesis was that such a species would be aromatic, a bis -homoaromatic species to be precise, itself an interesting variation on the normal theme of aromaticity.

Semibullvalene is an unsettling molecule. Whilst it has a classical structure describable by a combination of Lewis-style two electron and four electron bonds, its NMR behaviour reveals it to be highly fluxional. This means that even at low temperatures, the position of these two-electron bonds rapidly shifts in the equilibrium shown below. Nevertheless, this dynamic behaviour can be frozen out at sufficiently low temperatures.