Regioselective C-H Hydroarylation of Internal Alkynes with Arenecarboxylates: Carboxylates as Deciduous Directing Groups

摘要

In the presence of catalytic [Ru(p-cym)I-2](2) and the base guanidine carbonate, benzoic acids react with internal alkynes to give the corresponding 2-vinylbenzoic acids. This alkyne hydroarylation is generally applicable to diversely substituted electron-rich and electron-poor benzoic and acrylic acids. Aryl(alkyl) acetylenes react regioselectively with formation of the alkyl-branched hydroarylation products, and propargylic alcohols are converted into gamma-alkylidene-delta-lactones. The hydroarylation can also be conducted decarboxylatively with a different choice of catalyst and reaction conditions. This reaction variant, which does not proceed via intermediate formation of 2-vinylbenzoic acids, opens up a regioselective, waste-minimized synthetic entry to vinylarenes.