Regioselective C−H Hydroarylation of Internal Alkynes with Arenecarboxylates: Carboxylates as Deciduous Directing Groups. (26th April 2016)

• Record Type: Journal Article
• Authors: Huang, Liangbin; Biafora, Agostino; Zhang, Guodong; Bragoni, Valentina; Gooßen, Lukas J.
• Is Part Of: Angewandte Chemie. Volume 128:Number 24(2016)
• Page Start: 7047
• Page End: 7051
• Publication Date: 2016-04-26
• Subjects: Alkine -- C-H-Aktivierung -- Decarboxylierungen -- Ruthenium -- Synthesemethoden; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201600894
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: In the presence of catalytic [Ru( p ‐cym)I2 ]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 γ‐alkylidene‐δ‐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.