Five-membered heterocyclic arenes account for a large portion of the heterocycles found in pharmaceuticals and bioactive molecules.1 Synthesis of heteroaryl halides and elaboration via metal catalysed cross coupling reactions- particularly with aliphatic amines- is, however, known to be challenging. These small heterocycles-particularly electron-rich systems- frequently coordinate to palladium, promoting catalyst deactivation via displacement of the supporting

The importance of methylation in the discovery and development of bio-active small molecules is well known. I presented a webinar a couple of years ago on the “The magic methyl in medicinal chemistry,” demonstrating the unique properties of this, the simplest functional group.1 I also reviewed the state of the art in synthetic approaches to