Highly E-selective all-carbon tetrasubstituted alkenes with a C(sp(3))-F unit have been synthesized through a dehydroxyfluorination of Morita-Baylis-Hillman (MBH) adducts which can be readily prepared from alpha,beta-unsaturated carbonyl compounds and a-keto esters. A variety of subsequent transformations afforded monofluoromethyl substituted heterocycles in high yields.