I want to talk about two user-friendly aromatic substitutions today. While the mechanisms are entirely different, there is a common link. Both of these reactions made a difference in our approaches to either making or modifying halogenated aromatics. The first reaction is the aromatic bromination process that requires a curious combination of triphenylphosphine sulfide catalyst, an aromatic compound, and N-bromosuccinimide. My PhD student Sean Liew found this remarkably mild process in Gustafson’s Org Lett paper. I can highly recommend this reaction, whose only downfall is the production of phosphorous-based by-products. I don’t think that the role of triphenylphosphine sulfide has been fully delineated, if that is what you are interested in.

http://pubs.acs.org/doi/abs/10.1021/acs.orglett.5b00186

The other process is separated from the one above by 8 years. This is when Lilu Yu was doing her Masters degree in my lab and was in need of a mild method to replace aromatic fluorine by the hydroxyl group. I remember this process to be an excellent way to deliver the hydroxide nucleophile, although in a somewhat convoluted way. We used this chemistry, originally described by Green, when nothing else worked, so I would highly recommend this process.

http://www.sciencedirect.com/science/article/pii/S0040403902005610