Late Stage Functionalization of Secondary Amines via a Cobalt-Catalyzed Electrophilic Amination of Organozinc Reagents.

A general preparation of polyfunctional hydroxylamine benzoates from the corresponding secondary amines is reported. This convenient synthesis allows the setup of a late-stage functionalization of various secondary amines, including pharmaceuticals and peptidic derivatives. Thus, a cross-coupling of hydroxylamine benzoates with various alkyl-, aryl-, and heteroaryl-zinc chlorides in the presence of 5 mol % CoCl (25 °C, 2 h) provides a range of polyfunctional tertiary amines. This method was used to prepare penfluridol and gepirone.