Efficient construction of novel α-keto spiro ketal and the total synthesis of (±)-terreinol

The first total synthesis of (±)-terreinol is described. An intramolecular Pd(II)-catalyzed cycloisomerization of a 2-(1′-alkynyl)benzyl alcohol via an apparent 6-endo diagonal pathway led to the 1H-isochromene ring system, which was further converted to the desired spiro ketal via an iodine-mediated intramolecular spiro-cyclization.