A nice proof of concept here at The Angewandte exploiting the Leidenfrost effect in a chemical reaction. Ryan Bain et al. have asked themselves the question: can a reaction accelerate when confined to a tiny droplet levitating on a hot surface?
The experimental setup was a simple petri dish on top of a heater at 500°C. The reagents were isatin and phenylhydrazine with some HCl added forming the hydrazone. The solvent was methanol and the droplet size 0.5 mL. After 2 minutes the reaction was done and ready for electrospray ionization (ESI) analysis. The reaction turns out to be six times as fast as the bulk reaction!
The same reaction is known to be accelerated inside the same ESI machine when the time-of-flight between source and mass spectrometer of the droplets is increased. In both cases the effect is the result of solvent evaporation and increased concentrations. Temperature does not play a role as the expected temperature inside a droplet does not exceed 45°C. The reaction preferably takes places at the solvent air interface. The smaller the droplet the larger the acceleration, adding a surfactant killed the kinetic effect.
08 July 2016 - Gone in 60 minutes
Is this really oseltamivir total synthesis number 61? We stopped counting the last time at number 27. Soon there will be a Journal of Oseltamivir Synthesis. Hayashi & Ogasawara present effort no 61 in Organic Letters (DOI) and Time Is Money! The opening paragraph contains two non-truths: "It is one of the goals for a chemist to synthesize a molecule as quickly as possible" and Tamiflu "is one of the most effective drugs for the treatment of influenza". But never mind, the big claim in this effort is a one-pot synthesis in just 60 minutes at the cost of an overall yield of just 15%. In a single reactor were added sequentially (the big picture): a nitroalkene and an aldehyde in an asymmetric Michael addition with reagents a proline / thiourea / formic acid catalyst system, an ethyl acrylate for an Horner-Wadsworth-Emmons reaction, TBAF for nitro groupepimerisation and zinc (under microwave irradiation) for a final reduction.