Regioselective Direct C−H Phosphorylation of Benzofulvenes

A practical and straightforward protocol to access site-selective C-3 phosphorylated benzofulvenes by means of cross-dehydrogenative coupling of two nucleophilic moieties, employing silver as a promoter, is described here. Remarkably, this protocol provides a broad, structurally diverse phosphorylated benzofulvene. Initial mechanistic studies shed light on its radical coupling nature, and late-stage transformations offer highly diversified benzofulvenes core.