This caught my eye while reading Tetrahedron this morning. At first I thought it was a mistake, but then I realised that it was also in the PDF as well, presumably okayed by the authors. I think it's pretty funny to see this title in the TOC with 'Orginal Research Article' next to it:
Strangely, the rest of the paper seems quite confident. I guess time will tell.
Physics Nobel Laureate, legendary teacher and all-round cool guy Richard Feynman once said: “[There’s a] difference between knowing the name of something and knowing something”. This is true in a whole range of fields, and we’ve probably all seen enough students confidently assert that a particular step is “just a simple named reaction”, only to completely crumble when asked the mechanism or conditions. Still, I think named reactions are a great way of learning some really important chemistry that can then be applied to many other things. A chemist who knows, say, the fifty most common named reactions and a decent chunk of basic theory will be in a good position to take a guess at the mechanism of most things they encounter. They're also a useful conversational shorthand if you want to convey how something works without reaching for a pen and paper. Very few reactions are so obscure and ‘out there’ that they’re not at least conceptually related to things we all know well. For example, I set this as part of a group problem session I ran last week:
For the last planned post in my Unnatural Products series, I’m going to write about Eaton’s 1981 synthesis of pentaprismane. At the time, unnatural hydrocarbons were hot targets, and as the next largest prismane on the list this target was the subject of much research by groups around the world. Perhaps Eaton's biggest rivals were the groups of Paquette and Petit, and in fact all three had, at various times, synthesised hypostrophene as an intended precursor to the target.
Unfortunately, the ‘obvious’ [2 + 2] disconnection from pentaprismane turned out to be a dead end and the photochemical ring closure was unsuccessful. The 1970s and early 1980s saw the publication of a number of other similarly creative, but sadly ill-fated, approaches based on various ring contractions, and the compound gained a well-earned reputation for extraordinary synthetic inaccessibility.
Second in my somewhat badly thought out Unnatural Products series is dodecahedrane. To be honest, this compound is actually pretty much the main reason for this series. I only found out it had been made at the start of the year (even though Paquette did it way back in 1983), and it blew my mind. I mean look at it – where do you even start? It took me a full hour to draw the damn thing in Chemdraw, and I still can't get it to look right on paper. As Paquette himself said in an abstract ‘the aesthetically pleasing symmetry of the dodecahedral framework was clearly apparent’. In common with the syntheses of the other two compounds above the route involved both Diels-Alder reactions and lots of photochemistry. Let’s take a look.
There are exactly five regular polyhedrons that can be made, and as they were first discussed in detail by Plato, they’re sometimes known as the platonic solids. Now, you might not have heard of them under that name, but I’m pretty sure most of them are familiar to chemists. In order of increasing size, the series starts with the tetrahedron, the shape of stereogenic centres at carbon, and the source of asymmetry in life. In fact, Jacobus Henricus van 't Hoff won the very first Nobel prize in chemistry ever back in 1901 for being one of the first to notice this. Although the parent hydrocarbon has yet to be synthesised, a number of tetrahedrane derivatives have been reported. Next comes the cube, the corresponding hydrocarbon of which, cubane, was famously first synthesised by Eaton back in 1964. Third up is the octahedron, more of an inorganic chemist's shape and rather unlikely to ever exist with a carbon skeleton due to the crazy C-C bond angles required. Fourth, the dodecahedron, has actually been better studied by organic chemists than most people realise and, after much competition, Leo Paquette was the first to synthesise the corresponding hydrocarbon in 1983. Last and largest in the series is the icosahedron, which I can’t think of a way to link to chemistry, but we’re certainly unlikely to ever see a carbon based version as all the atoms in the skeleton need to have five bonds.
In this post and the next two I’m going to discuss three syntheses; those of the two platonic solids made to date (cubane and dodecahedrane), and that of the non-regular polyhedron pentaprismane, because it’s also pretty cool. Why do this? Well, when if you consider, say, dodecahedrane in a retrosynthetic sense then unless you lived through the era when these compounds were fashionable targets, have studied them, or are a bit of a genius then it's not obvious where to start so hopefully we can learn a bit of chemistry. I also enjoy a bit of chemical history and some of the methods used were pretty neat as we'll see.