Chemoselective Diazotransfer of Primary Aliphatic Amines into Azides Using Commercial Aryl Sulfonyl Azides.

Here, we report that commercial aryl sulfonyl azides efficiently convert primary aliphatic amines into azides under mild conditions. We further show that this diazotransfer reaction exhibits a pronounced preference for aliphatic over aromatic amino groups. This chemoselectivity enables the one-step synthesis of bifunctional molecules bearing both azido and aniline moieties, offering a practical and scalable route to orthogonally "clickable" building blocks for chemical biology and materials modification.