Continuing an exploration of the mechanism of this reaction, an alternative new mechanism was suggested in 1989 (having been first submitted to the journal ten years earlier!). Here the key intermediate proposed is a thiirenium cation (labelled 8 in the article) and labelled Int3 below.

Sometimes a (scientific) thought just pops into one’s mind. Most are probably best not shared with anyone, but since its the summer silly season, I thought I might with this one.

The Willgerodt reaction, discovered in 1887 and shown below, represents a transformation with a once famously obscure mechanism. A major step in the elucidation of that mechanism came using the then new technique of 14C radio-labelling, shortly after the atom bomb projects during WWII made 14CO2 readily available to researchers.

One of the most fascinating and important articles dealing with curly arrows I have seen is that by Klein and Knizia on the topic of C-H bond activations using an iron catalyst.

Metaldehyde is an insecticide used to control slugs.

With the current global lockdown, and students along with everyone else staying at home, I have noticed some old posts of mine are getting more attention than normal. One of these is an analysis I did in 2012 of Robinson’s original curly arrow illustration.

My previous two posts on the topic of strongest bonds have involved mono and diprotonating N2 and using quantum mechanics to predict the effect this has on the N-N bond via its length and vibrational stetching mode. Such species are very unlikely to be easily observed for verification.

I occasionally notice that posts that first appeared here many years ago suddenly attract attention.

Earlier, I explored the choreography or “timing”, of what might be described as the curly arrows for a typical taught reaction mechanism, the 1,4-addition of a nucleophile to an unsaturated carbonyl compound (scheme 1). I am now going to explore the consequences of changing one of the actors by adding the nucleophile to an unsaturated […]

A little more than a year ago, a ChemRxiv pre-print appeared bearing the title referenced in this post, which immediately piqued my curiosity. The report presented persuasive evidence, in the form of trapping experiments, that dicarbon or C2 had been formed by the following chemical synthesis.

In a previous post, I talked about a library of reaction pathway intrinsic reaction coordinates (IRCs) containing 115 examples of organic and organometallic reactions.