Construction of Biaryl Skeletons Initiated with Benzyne Insertion into C═S Double Bond of Pyridine‐2(1 H )‐thiones

Abstract Benzyne insertion reactions have become a versatile strategy for introducing diverse functional groups onto the benzene ring under transition‐metal‐free conditions. However, research on employing this method to introduce aryl/alkenyl groups onto the benzene ring is rather limited, with constrained structural scopes. Here, biaryl skeletons are readily prepared by harnessing the insertion of benzyne into C═S double bond of pyridine‐2(1 H )‐thiones, where a pyridyl and an arylthio or alkenylthio group are simultaneously introduced on the formal triple bond of a benzyne. It is worth noting that these compounds can not only be further derivatized into 1,2‐diarylbenzenes or 2‐alkenyl‐1,1′‐biaryls via desulfurization, but can also form various complexes with different metals through diverse coordination modes.