Some of the most amusing dynamics in science happen when a given field becomes overcrowded. Many factors contribute to the exponential increase in attraction to a given problem. These factors range from the innate significance of questions that need to be resolved to the low barrier for entry. In the latter case, there is a chance to make rapid gains with fairly modest expenditures. I would submit that every research field has some skeletons in its closet. The area of C-H activation has certainly been a very popular arena for innovation, delivering new ways to construct molecules. But what about some skeletons from the closet in this field? In my mind, such skeletons would correspond to foundational contributions made a long time ago, yet lost in the tidal wave of papers everyone thinks should be cited. A case in point is an important report by Rawal and co-workers published in the Journal of Organic Chemistry in… 1997. That’s right, way before the whole craze took over the synthetic organic community. Take a look at this fine piece of research and see what you think. I suppose many of you might have an eyebrow (or two) raised when you see the content of this report and then consider the year it was published in. I am not saying that this paper is not being cited, I am just saying that it is probably not mentioned often enough, at least in the talks I have recently attended at various conferences. A good friend of mine brought this manuscript to my attention.
if the leaving group is diazonium salt and the metal catalyst is “bronze” copper alloy powder, you can find examples of this CH activation Ar-Ar intramolecular coupling reaction going back almost a century… I think it is even is a named reaction.
Well, that is true – of course! I am just referring to palladium here.
These kinds of “aryl Heck” reactions go back even much further. Here is just one example from 1992. It doesn’t even merit a mention as a key step or a citation – I think that “back then” these kinds of intramolecular Heck reactions were not that surprising.
Thanks a lot, Jeff – this is interesting and important. Would love to read the reference, but for some reason I do not see a link.
Sorry, I’m a little new at this. I’ll try to post it this way:
I’m sure such reactions must go back further, but no chance to chase it the origin just now.
That is excellent. Thanks!
we made a molecular motor using this kind of chemistry
see pg 7 of the SI – we didn’t we didn’t even reference anyone
Thanks for bringing this up – I have always really enjoyed this chemistry.