The reductive cross-coupling of 1,3-dioxolane with carbonylcompounds to yield α-hydroxy aldehyde derivatives was attained by the reduction of iodobenzene with a solution of SmI2 in 1,3-dioxolane-CH3CN-HMPA (20:2:1) in the presence of carbonylcompounds under extremely mild conditions. The process seems to involve 1,3-dioxolanyl radical intermediate.