The Curtius reaction is represented in most chemistry texts and notes as following path (a) below. It is one of a general class of thermally induced rearrangement which might be described as elimination/migration (in a sense similar to this ring contraction migration/elimination), in this case implicating a nitrene intermediate if the two steps occur consecutively.

organic chemistry. It does not look like much, but this small little molecule brought us ferrocene, fluxional NMR, aromatic anions and valley-ridge inflexion points. You might not have heard of this last one, but in fact I mentioned the phenomenon in my post on nitrosobenzene. As for being at a crossroads, more like a Y-junction. Let me explain why.

The reaction between a carbene and an alkene to form a cyclopropane is about as simple a reaction as one can get. But I discussed before how simple little molecules (cyclopropenyl anion) can hold surprises. So consider this reaction: Transition state for reaction between ethene and dichlorocarbene.

The mechanism of the reaction of alkenes known as ozonolysis was first set out in its modern form by Criegee. The crucial steps, (a), (b) and (d), are all pericyclic cycloaddition/eliminations.

In the previous post, I went over how a reaction can be stripped down to basic components. That exercise was essentially a flat one in two dimensions, establishing only what connections between atoms are made or broken. Here we look at the three dimensional arrangements. It all boils down to identifying what the stereochemistry of the bonds marked with a wavy line are. To make it simple, let us start with the molecule shown on the left.

Its a bit like a jigsaw puzzle in reverse, finding out to disassemble a chemical reaction into the pieces it is made from, and learning the rules that such reaction jigsaws follow. The following takes about 45-50 minutes to follow through with a group of students.

I left the story of the molecule below on the precipice of a cliff. I had shaved off the four benzo groups (blue) in the time honoured computational tradition of clearing away distractions. Unfortunately, it became clear as the story unfolded that the benzo groups had a distractingly critical role to play, and so its time to start adding them back again, but in stages.

A feature of many a classic review article is that not only does it organise and rationalise existing literature, but it will predict new chemistry as well. I have already noted Woodward and Hoffmann’s (WH) review as achieving the former, and here I take a (sideways) look at one of their predictions.

The previous post showed how the 2+2 cycloaddition of an alkene could occur by a sort of sideways insinuation of the bonds. I have also shown how the same reaction can occur with a dramatic rotation of one of the double bonds. This post compares the two moves side by side. 0.0 5.3 kcal/mol The forbidden dance The allowed dance. As is sometimes the case in real life, the forbidden option has the lower activation barrier!

In this earlier post, I described how the stereochemistry of π2+π2 cycloadditions occurs suprafacially if induced by light, and how one antarafacial component appears if the reaction is induced by heat alone.