Nickel-Catalyzed Desulfurative Cross-Coupling of Aryl Iodides with Heteroaromatic Thioethers via C–S Bond Cleavage

Herein, we present a Ni-catalyzed direct cross-coupling of heteroaromatic thioethers with aryl iodides via selective C(sp²)-S bond cleavage under reductive conditions, thereby providing various biaryl frameworks with high efficiency. Mechanistic studies suggested Mo(CO)₆ played a crucial role in facilitating the activation of the C(sp²)-S bond. This protocol demonstrated a wide substrate scope, operational simplicity, and good functional group compatibility. Furthermore, the utility of this reaction was highlighted by facile scale-up and sequential modification of heteroaryl frameworks.