The lithiation of primary and secondary dialkyl sulfates with an excess of lithium powder in the presence of a catalytic amount of naphthalene at -78-degrees-C leads to the corresponding alkyl-lithium reagents (1:2 molar ratio), which react with different electrophiles, mainly carbonyl compounds. to yield the expected coupling products. This methodology represents an indirect way for transforming alcohols into organolithium compounds through the corresponding dialkyl sulfates.