title: Palladium-catalyzed intermolecular addition of formamides to alkynes.
abstract: A novel palladium system for an intermolecular addition of formamides to alkynes has been developed. The reaction of formamides with internal alkynes in the presence of a palladium catalyst with acid chloride as an additive afforded (E)-alpha,beta-unsaturated amides regio- and stereoselectively. The same catalyst system realized the first example of the addition of formamides to terminal alkynes giving the corresponding alpha,beta-unsaturated amides bearing a terminal methylene moiety as major products. The present reaction was widely applicable to substrates with various functionalities. This method also could be applied to the reaction of N,N-disubstituted formamides with norbornene. A hydridopalladium species would be formed as a key intermediate with in situ generated HCl under the reaction conditions.
authors.affiliation: Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan.
authors.forename: Tetsuaki
authors.initials: T
authors.lastname: Fujihara
authors.forename: Yuko
authors.initials: Y
authors.lastname: Katafuchi
authors.forename: Tomohiro
authors.initials: T
authors.lastname: Iwai
authors.forename: Jun
authors.initials: J
authors.lastname: Terao
authors.forename: Yasushi
authors.initials: Y
authors.lastname: Tsuji