Radical-based functionalization-oriented construction: rapid assembly of azaarene-substituted highly functionalized pyrroles.

Totally different functionalization and construction as two fundamental synthetic protocols have long been applied to furnish azaarene variants. Here, a novel radical-based functionalization-oriented construction strategy by exploiting the electronic properties of azaarenes and the high reactivity of radicals is developed. Under a photoredox catalysis platform, the robust ability of such an artful combination of functionalization with construction is disclosed in the synthesis of valuable 3-azaarene-substituted densely functionalized pyrroles. In addition to the ability to use the readily accessible feedstocks, the high synthetic efficiency and the good functional group tolerance, the substrate scope is broad (81 examples) resulting from the capability to flexibly replace the types of azaarenes and other substituents. Control experiments and density functional theory (DFT) calculations elucidate the plausible mechanism involving the reaction pathways and the important role of NaHPO as an additive in the reaction.