Treatment of terminal olefins bearing electron-withdrawing groups with (R, R)-pentane-2, 4- diol (2) in the presence of PdCl2–CuCl–O2 in 1, 2-dimethoxyethane gives cyclic acetals such as (3) and (12b) via attack at the terminal carbon atom; the corresponding acetals are similarly formed from propane-1, 3-diol (5) and ethylene glycol (8).