In the presence of a catalytic amount of LiCl, alpha-dimethylsilylesters (alpha-DMS-esters) 1 smoothly reacted with various aldehydes at 30 degrees C to give aldols in good to high yields. On the other hand, the aldol reaction with ketones was effectively promoted by MgCl2 rather than by LiCl. alpha-Enones also underwent the metal chloride-promoted addition of 1 at the carbonyl carbon or beta-carbon.