Thermal and Photoinduced Radical Cascade Annulation using Aryl Isonitriles: An Approach to Quinoline‐Derived Benzophosphole Oxides

Abstract Herein, we present a radical cascade addition cyclization sequence to access quinoline‐based benzophosphole oxides from ortho ‐alkynylated aromatic phosphine oxides using various aryl isonitriles as radical acceptors and inexpensive tert ‐butyl‐hydroperoxide (TBHP) as a terminal oxidant in the presence of a catalytic amount of silver acetate. Alternatively, the same cascade can be realized through a sustainable photochemical approach utilizing 1,2,3,5‐tetrakis(carbazol‐9‐yl)‐4,6‐dicyanobenzene (4CzIPN) as an organic photocatalyst at room temperature. The introduced modular approach shows broad functional group tolerance and offers straightforward access to complex P,N ‐containing polyheterocyclic arenes. These novel π‐extended benzophosphole oxides exhibit interesting photophysical and electrochemical properties such as absorption in the visible region, emission and reversible reduction at low potentials, which makes them promising for potential materials science applications. The photophysical properties can further be tuned by the addition of external Lewis and Brønsted acids.