Palladium-Catalyzed Dearomative Heck/C(sp2)–H Activation/Decarboxylative Cyclization of C2-Tethered Indoles

Until now, palladium-catalyzed dearomative Heck reactions of indoles were largely limited to β-H elimination and nucleophilic capture of the transient alkyl-Pd(II) species. Herein, we disclose a novel palladium-catalyzed dearomative Heck/C(sp²)-H activation/decarboxylative cyclization of C2-tethered indoles. In this protocol, the alkyl-Pd(II) species formed by dearomatization of C2-tethered indoles is not terminated by common β-H elimination or nucleophilic capture, but rather generates C,C-palladacycle via C-H activation. The latter is intercepted by α-bromoacrylic acids to produce pentacyclic and heptacyclic fused indolines.