Abstract
The cyclization of trans-δ-hydroxy enones to cyclic mixed ketals routinely requires superstoichiometric strong acid. By operating under a photoisomerization regime, the cyclization of trans-δ-hydroxy enones proceeds under catalytic Brønsted acid to provide cyclic ketals or unsaturated spiroketals in a highly diastereoselective fashion. A one-pot, two-step protocol was thus developed to provide cyclic methoxy ketals with a free β-hydroxy group for future functionalization.