Palladium‐Catalyzed Efficient Synthesis of Benzofuro[3,2‐<i>b</i>]Pyrroles and Pyrrolo[3,2‐<i>b</i>]Indoles: Access to Nitrilo Substituted Benzofuro[3,2‐<i>b</i>]Indoles and Indolo[3,2‐<i>b</i>]Indoles Using DDQ

We report an elegant method for the construction of fused pyrrole rings via palladium-catalyzed reactions of aryl iodides with N-prop-2-ynylated 3-aminobenzofurans/3-aminoindoles leading to the general synthesis of benzofuro[3,2-b]pyrroles/pyrrolo[3,2-b]indoles via 3-(arylidene)-2,3-dihydro intermediates. Exposing the intermediates to 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) delivered benzofuro[3,2-b]indoles (BFIs) and indolo[3,2-b]indoles (IIs) containing vicinal cyano groups. These transformations constitute a rapid intermolecular assembly through several carbon - carbon bond forming reactions, involving a single electron transfer (SET) process in the crucial steps. Photophysical studies of selected products identified promising candidates for future applications.