Reaction of triethyl phosphite with a series of α, β-unsaturated esters, ketones, aldehydes, amides and nitriles in protonating solvents proceeds smoothly to furnish β-substituted phosphonate esters. This process, termed hydrophosphinylation, is quite general in contrast to reduction and reductive dimerization, the alternative reaction pathways previously observed for dibenzoylethylene. The most active olefins (methyl vinyl ketone, ...