A Pd-catalyzed decarboxylative dearomatization reaction of a heterocyclic substrate enables access to an uncommon reaction intermediate that rearomatizes in the presence of amine bases in a net C-H functionalization sequence. The dearomatized benzo[]thiophene intermediate bears an exocyclic alkene that can be functionalized through cycloaddition and halogenation reactions to deliver complex heterocyclic products.
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Palladium-Catalyzed Dearomative Heck/C(sp)-H Activation/Decarboxylative Cyclization of C2-Tethered Indoles.
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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(sp)-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 ,-palladacycle via C-H activation.
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