In organic chemistry, a Hiyama coupling is a palladium or nickel-catalyzed cross coupling reaction of organosilanes with organic halides or triflates. Hiyama couplings were first reported by Yasuo Hatanaka and Tamejiro Hiyama in 1988.
Typically, the Hiyama coupling reaction is promoted by activation of the organosilane with fluorides. The reaction possesses many advantages such as low environmental impact, high atom efficiency, and safe handling compared with the coupling reactions of organoboron, organozinc, or organotin compounds.
In the original 1988 publication 1-iodonaphthalene was reacted with trimethylvinylsilane to produce 1-vinylnaphthalene with allylpalladium chloride dimer as catalyst, HMPA as solvent and TASF reagent as fluorine source.
The reaction proceeds through the usual oxidative addition , transmetalation, trans-cis isomerization and reductive elimination sequence. The purpose of the fluoride is to activate the silicon compound RSiR'3 to a RSi-R'3F intermediate which is more amenable to transmetalation. Without the added fluorine the organosilicon compound is simply too stable.