Fluoride-mediated phosphination of alkenes and alkynes by silylphosphines

Regioselective phosphination of carbon–carbon unsaturated bonds by a fluoride-mediated reaction of silylphosphines is described. Alkenes and alkynes having a directing group, such as an aromatic or a carbonyl group, reacted to form a carbon–phosphorus bond under mild conditions. When an anhydrous fluoride source was applied in the presence of an electrophile, the corresponding three-component coupling product was obtained.