ja910038p_si_002.cif (34.45 kB)
Palladium-Catalyzed Intermolecular Addition of Formamides to Alkynes
dataset
posted on 2010-02-17, 00:00 authored by Tetsuaki Fujihara, Yuko Katafuchi, Tomohiro Iwai, Jun Terao, Yasushi TsujiA 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)-α,β-unsaturated amides regio- and stereoselectively. The same catalyst system realized the first example of the addition of formamides to terminal alkynes giving the corresponding α,β-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.