Pd-Catalyzed Chemodivergent Monodefluorinative Cascade Cyclizations of gem-Difluorovinyl-Conjugated Alkynylanilines to Fluorinated Benzocarbazoles and Indoloisoquinolines.

An efficient one-pot Pd-catalyzed reaction medium-directed chemodivergent protocol has been developed that enables the controlled assembly of meta-fluorinated benzocarbazoles, fluoroindoloisoquinolines, and their halogenated analogues from easily synthesizable gem-difluorovinyl-conjugated alkynylanilines (gem-DFAA). The protocol exhibits a broad spectrum of substrate scope including late-stage coupling of fluorobenzocarbazoles with anti-inflammatory drugs and the synthesis of fluorinated analogues of inhibitors for estrogen receptors.