Selective Synthesis of Pyrano[3,2-b]indoles or Cyclopenta[b]indoles Tethered with Medium-Sized Rings via Cascade C-C σ-Bond Cleavage and C-H Functionalization.

Highly atom-economical tandem reactions have been developed for the synthesis of pyrano[3,2-b]indoles or cyclopenta[b]indoles tethered with 7-, 8-, or 9-membered rings. These reactions first undergo a carbon-carbon σ-bond cleavage reaction of cyclic β-ketoesters. Next, in the presence of CuCl2 and Ag2CO3, intramolecular O-H/C-H coupling occurs to give pyrano[3,2-b]indoles. This is the first example for capture of the enoloxyl radical of the intramolecular C-O bond formation reaction, whereas C3 nucleophilic addition afforded cyclopenta[b]indoles using TsOH·H2O.