In the presence of water, titanocene(III) complexes promote a stereoselective C-C bond-forming reaction that provides
-lactols by radicalcoupling between aldehydes and conjugated alkenals. The method is useful for both intermolecular reactions and cyclizations. The relativestereochemistry of the products can be predicted with confidence with the aid of model Ti-coordinated intermediates. The procedure can becarried out enantioselectively using chiral titanocene catalysts.