Borrowing hydrogen from alcohol, storing it on the catalyst and subsequent transfer of the hydrogen from catalyst to an in situ generated imine is the hallmark of a transition metal...

We demonstrate that an in situ generated di-reduced phenalenyl (PLY) species accumulates sufficiently high energy and acts as a super electron donor to generate aryl radicals from aryl halides to accomplish Buchwald–Hartwig-type C–N cross-coupling reactions at room temperature. This catalytic protocol does not require any external stimuli such as heat, light, or cathodic current. This protocol shows a wide variety of substrate scope covering different genres of aryl and heteroaryl halides with various aromatic as well as aliphatic amines and late-stage functionalization of the well-known natural products. The control experiments, along with extensive density functional theory (DFT) calculations, unveil that the aryl radical is generated by a single electron transfer from the di-reduced PLY to the aryl halide substrate. The aryl radical acts as an electrophile and binds with amine, leading to the chemically driven radical-mediated C–N cross-coupling under transition-metal-free conditions.

New and efficacious phenalenyl based Pt(ii) compounds have been used to design an “easy to use tool” for mechanistic understanding.