Pd-catalyzed Reactions Involving Arynes

This review aims at providing synthetic organic chemists with enough background for research in the palladium-catalyzed chemistry of highly reactive aryne species obtained in situ by the attack of a fluoride ion on (o-trimethylsilyl)aryl triflates under mild reaction conditions. The chemistry generally involves oxidative addition of Pd(0) to the aryne or the organic halide or triflate and subsequent insertion of the aryne, alkyne, alkene or carbon monoxide, followed by various organic transformations to give substituted arenes, bicyclic products, heterocycles and polycyclic aromatic hydrocarbons. Palladium-catalyzed aryne annulations involving arynes, alkynes, aryl or vinylic halides and triflates, multicomponent couplings, and σ-bond insertions are the main focus, but other reactions, which do not fall under these categories, will be discussed along with an overview of the mechanistic pathways involved.