Two years ago, I discussed how curly arrow pushing is taught, presenting four different ways of showing the arrows. One of the comments posted to that blog suggested that all of the schemes shown below were deficient in one aspect.
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.
Recollect, Robinson was trying to explain why the nitroso group appears to be an o/p director of aromatic electrophilic substitution. Using σ/π orthogonality, I suggested that the (first ever) curly arrows as he drew them could not be the complete story, and that a transition state analysis would be needed. Here it is.
A month or so ago at a workshop I was attending, a speaker included in his introductory slide a QR (Quick Response) Code. It is a feature of most digital eco-systems that there is probably already “an app for it”. So I thought I would jump on the band wagon by coding an InChI string.
I blogged about this two years ago and thought a brief update might be in order now. To support the discussions here, I often perform calculations, and most of these are then deposited into a DSpace digital repository, along with metadata.
The discussion appended to the post on curly arrows is continued here.
Little did I imagine, when I discovered the original example of using curly arrows to express mechanism, that the molecule described there might be rather too anarchic to use in my introductory tutorials on organic chemistry. Why? It simply breaks the (it has to be said to some extent informal) rules!
Twenty years are acknowledged to be a long time in Internet/Web terms.
I was first taught curly arrow pushing in 1968, and have myself taught it to many a generation of student since. But the other day, I learnt something new.
In the preceding post, I described a fascinating experiment and calculation by Bogle and Singleton, in which the trajectory distribution of molecules emerging from a single transition state was used to rationalise the formation of two isomeric products 2 and 3. In the present post, I explore possible consequences of including a sodium cation (X=Na+ below) in […]
Singleton and co-workers have produced some wonderful work showing how dynamic effects and not just transition states can control the outcome of reactions. Steve Bachrach’s blog contains many examples, including this recent one.