Herein, we present a Ni-catalyzed direct cross-coupling of heteroaromatic thioethers with aryl iodides via selective C(sp)-S bond cleavage under reductive conditions, thereby providing various biaryl frameworks with high efficiency. Mechanistic studies suggested Mo(CO) played a crucial role in facilitating the activation of the C(sp)-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.

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http://dx.doi.org/10.1021/acs.joc.4c00678DOI Listing

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