Deconstructive dicarbofunctionalization of cyclic amines enabled by C–H and C–N bond activation†

The incorporation of nitrogen-containing heterocycles by the deconstruction of cycloamines with nucleophiles represents a powerful method in organic synthesis. However, this paradigm faces severe challenges in the simultaneous construction of C–N and C–C bonds that are typically encountered in pharmaceuticals. Herein, a metal- and catalyst-free C–N and C–H bond activation reaction mediated by a haloarene-derived aryne intermediate is identified that enables the deconstructive dicarbofunctionalization of cyclic amines. With this facile method, a variety of amines can undergo direct dicarbo-functionalization reactions with highly accessible aryl halides and hydrocarbons, yielding N-arylpiperazines and functionalized arylamines with great potential as drug candidates.