Recent advances in the oxidation-reduction condensation reaction of alkyl phosphinites are described. The carbon-sulfur, carbon-carbon, or carbon-nitrogen bond forming reactions and cyanation, isocyanation reactions are established. These reactions proceed through inversion of configuration even when tertiary alkyl phosphinites are employed, providing thus, a novel route to chiral hydrosulfides, amines, nitriles, and isocyanides from easily available chiral alcohols.