Regioselective ring opening of unsymmetrical cyclic ethers with the A1C13-NaI-acetonitrile system: Application to hydroxylation of ent-kaurene.

Unsymmetrically substituted 5-membered cyclic ethers were effectively cleaved with the A1C1₃-NaI-CH₃CN system at the less hindered carbon atom to afford δ-iodoalcohols. Conversion of ent-kaurene to ent-14α- and ent-12β-hydroxykaurene was achieved through the ring opening of the cyclic ether with the present system as a key step.