Sulfones and sulfonamides with an α-CH bond can be easily alkylated by aliphatic alcohols to add the carbon skeleton of the alcohol via a one-step, Ru(II)-catalyzed redox neutral reaction. The reaction requires a substoichiometric amount of base and produces only water as a byproduct. Several pharmaceutically relevant functional groups such as piperidine, morpholine, etc. are well-tolerated under the reaction conditions to give higher value-added products in one step from widely available substrates. The reaction proceeds through a sulfone carbanion addition to an in-situ-generated aldehyde formed via catalytic dehydrogenation and subsequent catalyst-mediated replacement of the secondary alcohol by hydrogen.