Diverse Functionalization of Tetrahydro-β-carbolines or Tetrahydro-γ-carbolines via Oxidative Coupling Rearrangement.

We report herein diverse functionalization of tetrahydro-β-carbolines (THβCs) or tetrahydro-γ-carbolines (THγCs) via oxidative coupling rearrangement. The treatment of THβCs or THγCs with t-BuOOH (TBHP) afforded 3-peroxyindolenines, followed by HCl catalyzed indolation to form unexpected 2-indolyl-3-peroxyindolenines. Further rearrangement of these peroxides allows for rapid access to a skeletally diverse chemical library in good to excellent yields.