Sequential direct S_NAr reactions of pentafluorobenzenes with azole or indole derivatives

Sequential regioselective N-arylations through high-yielding catalyst-free direct S_NAr reactions of pentafluorobenzene derivatives with azole or indole derivatives are described. The N-arylated derivatives were further functionalized through a microwave-assisted cross-coupling reaction via C-H bond activation or Suzuki conditions. The order of the reactions could be reversed, proving full orthogonality between the reactions which led to well-defined fully substituted benzene derivatives.