alpha,alpha-Bis(dimethylsilyl)-substituted esters 1 were found to be quite valuable for alkenation of various aldehydes and ketones to alpha,beta-unsaturated esters. The reaction of aldehydes with 1 proceeded spontaneously in DMSO at 30 degrees C to give alpha,beta-unsaturated esters with good to high E selectivity. Under the same conditions, ketones were insensitive to 1; however, Li2SO4 and CaCl2 effectively accelerated their alkenation.