4-Arylhexahydroindole derivatives 5 were synthesized from 2-arylcyclohexenyl allylamine derivatives 4, which have a large protecting group on nitrogen, using zirconium-promoted cyclization. Reaction of 4e with Cp2ZrBu2, followed by treatment with MeMgBr and then O2, gave 2a in 63% yield by a one-pot reaction, since the approach of O2 to zirconium was prevented by the aryl group. The total syntheses of (±)-mesembrane and (±)-mesembrine ...