Posts Tagged ‘elimination’

The Curtius rearrangement. One step or two?

Monday, August 6th, 2012

The Curtius reaction is represented in most chemistry texts and notes as following path (a) below. It is one of a general class of thermally induced rearrangement which might be described as elimination/migration (in a sense similar to this ring contraction migration/elimination), in this case implicating a nitrene intermediate if the two steps occur consecutively. Wikipedia is normally very much on the ball with this sort of thing, and a comment about the reaction mechanism there notes that current evidence prefers route (b), avoiding nitrene intermediacy (and hence formally removing this from examples of nitrene reactions).

So time for a reality check (which in this case takes the form of a ωB97XD/6-311G(d,p)/SCRF=dichloromethane calculation). 

This is pretty clear-cut; no nitrene intermediate. Now for the standard text-books to catch up!