Tandem [4+2]/[2+2] Cycloaddition Reactions Involving Indene or Benzofurans and Arynes

The reaction of arynes with indene/benzofurans has been developed. The arynes were generated from 2(trimethylsilyl)aryl triflates by the fluoride-induced 1,2-elimination react with indene or various benzofurans proceeding via a cascade reaction involving the Diels-Alder reaction and a [2 + 2] cycloaddition reaction. The tandem process afforded functionalized dihydrobenzocyclobutaphenanthrenes in moderate to good yields. Moreover, the method has been utilized for the one-pot synthesis of benzo[b]fluoranthene.