Being doomed

I just came back from upstate New York, where I participated in the Northeast Regional Meeting of the ACS. The symposium I engaged in was superbly organized by Professor Anna Larsen of Ithaca College. This meeting gave me a chance to take a picturesque car ride from Toronto through the bucolic settings of upstate New York. These kinds of events are special because the audience is inevitably small, yet there is ample opportunity to see old friends and socialize with people you have not met. Peter Wipf (Pittsburgh), Scott Miller (Yale), Vladimir Gevorgyan (UIC), Amy Howell (Connecticut) and Alison Frontier (Rochester) made for a nice getaway from the daily routine.

I want to comment on something I wrote in my notes during the talk by Vladimir Gevorgyan. He made an interesting statement that an allene ketone of the type shown below (A) needs very “little” in order to get transformed into a furan. It appears that almost any metal catalyst is capable of inducing this transformation. Depending on the catalyst, the corresponding reaction might proceed by a unique mechanism, but the result in the same. I was really glad to learn about this phenomenon as it reminded me of my long-standing fascination with the “doomed” status of some molecules. This brings to mind the fundamental studies by Paul Schleyer. Back in the 1950s, he worked on the synthesis of adamantane and published an influential single-author JACS paper in which he described the transformation of the tricyclic hydrocarbon shown below into adamantane (see B). This work was followed by a number of papers from Paul’s lab, all pointing out different structures that somehow converged onto the adamantane nucleus when subjected to strong acid. The paths were different, but they had something in common: the involvement of cationic intermediates. Regardless of the specific chemistry, there are similar features in all transformations of what I call doomed molecules. The occurrence of reactions that bring a variety of structures to the same outcome is an interesting phenomenon and our appreciation of such pathways might be a sharpening stone against papers that are presumably innovative, yet correspond to inevitable outcomes driven by some strong forces.

2

http://pubs.acs.org/doi/abs/10.1021/ja01569a086

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