The lithiation of primary and secondary dialkyl sulfates with an excess of lithium powder in the presence of a catalytic amount of naphthalene (4 mol%) in THF at− 78° C leads to the corresponding alkyllithium reagents (1: 2 molar ratio) which react with different electrophiles, mainly carbonyl compounds, to yield after hydrolysis, the expected coupling products. This methodology represents an indirect way to transform alcohols into organolithium ...