(R)- or (S)-1-phenylprop-2-ynyl acetate was added stereoselectively to aldehydes to afford 4-hydroxy-1-phenylalk-2-ynyl acetates. The transformation of such adducts into the corresponding allylic 1,4-diacetates allowed a highly efficient transfer of chirality from C1 to C3 by a regio- and stereoselective [3,3]-sigmatropic rearrangement. The obtained unsaturated 1,2-diacetates were useful synthetic intermediates whose double bond and/or phenyl group were transformed in different aldehydes, acids, or esters.