Solvent-Controlled Switchable C–H Alkenylation of 4‑Aryl‑1H‑pyrrole-3-carboxylates: Application to the Total Synthesis of (±)-Rhazinilam

A solvent-controlled switchable C–H alkenylation of 4-aryl-1H-pyrrole-3-carboxylates via a Pd­(OAc)2 catalyzed oxidative Heck reaction was first realized. The corresponding C2 and C5 alkenylation products were obtained in good yields with high regioselectivities, respectively. The selective C5-alkenylation was successfully applied to the total synthesis of (±)-rhazinilam.