IBX (not Irritable Bowl Xyndrome)

I really like oxidation reactions but, for some reason, many students get confused about how they work. It's not really different than any other reaction. It's just electrons moving from one place to another. The problem is that we usually think it is weird to push electrons toward an oxygen at the same time break electrons off of an oxygen. However, in nearly every oxidation of alcohols, this is happening. Of course the requirement is that you have something attached to the oxygen that is more electrophilic. For example, highly oxidized Cr or S or, in the case of IBX or Dess Martin oxidations, I. Well, I saw this interesting paper in Angew. Chem. this week that used IBX to do an interesting double oxidation. It is a nice approach to the saxitoxin family of natural products. I thought I would share the mechanism for your edification. We don't often think about oxidizing past the ketone stage, but under enolization conditions and with the right structural features (beta nitrogen), you can oxidize the alpha carbon.

Iwamoto, O.; Koshino, H.; Hashizume, D.; Nagasawa, K., ACIEE, Early View