Through-Space 1,4-Palladium Migration and 1,2-Aryl Shift: Direct Access to Dibenzo[a,c]carbazoles through a Triple C-H Functionalization Cascade.

Abstract

A palladium-catalyzed expeditious synthesis of dibenzofused carbazoles from readily available 2-arylindoles and diaryliodonium salts is reported. Interestingly, after the electrophilic C3 palladation of indole, an unexpected "through-space" 1,4-palladium migration to the 2-aryl moiety, by remote C-H bond activation followed by C-H arylation with diaryliodonium salt, and an unprecedented 1,2-aryl shift take place. Finally, an intramolecular cross-dehydrogenative coupling (CDC) at the C2 position affords dibenzo[a,c]carbazoles in high yields. Remarkably, the present migratory annulation occurs through three C-H bond activation one C-C bond cleavage, and the simultaneous construction of three new C-C bonds in a single operation.