Skeletal Editing of Dibenzolactones to Fluorenes via Ni- or Pd-Catalyzed Decarboxylation

The skeletal editing of dibenzolactones to fluorenes by Ni- or Pd-catalyzed decarboxylation is reported. In contrast to previously reported intramolecular decarboxylative couplings, inductively electron-withdrawing ortho substituents on the aryl carboxylate moiety and metal additives are not required. The decarboxylation reaction proceeds cleanly and can be applied to the skeletal editing of a natural product analogue. Mechanistic observations are consistent with stabilization of the carboxylate-ligated Ni complex over the Ni-carboxylate ion pair, which is the key factor in promoting the challenging decarboxylation step in the catalytic cycle.