1095320-68-5Relevant academic research and scientific papers
Mechanistic investigation of the Ru-catalyzed hydroamidation of terminal alkynes
Arndt, Matthias,Salih, Kifah S. M.,Fromm, Andreas,Goossen, Lukas J.,Menges, Fabian,Niedner-Schatteburg, Gereon
, p. 7428 - 7449 (2011)
The ruthenium-catalyzed hydroamidation of terminal alkynes has evolved to become a broadly applicable tool for the synthesis of enamides and enimides. Depending on the catalyst system employed, the reaction leads chemo-, regio-, and stereoselectively to a single diastereoisomer. Herein, we present a comprehensive mechanistic study of the ruthenium-catalyzed hydroamidation of terminal alkynes, which includes deuterium-labeling, in situ IR, in situ NMR, and in situ ESI-MS experiments complemented by computational studies. The results support the involvement of ruthenium-hydride and ruthenium-vinylidene species as the key intermediates. They are best explained by a reaction pathway that consists of an oxidative addition of the amide, followed by insertion of a π-coordinated alkyne into a ruthenium-hydride bond, rearrangement to a vinylidene species, nucleophilic attack of the amide, and finally reductive elimination of the product.
Synthesis of secondary enamides by ruthenium-catalyzed selective addition of amides to terminal alkynes
Goossen, Lukas J.,Salih, Kifah S. M.,Blanchot, Mathieu
supporting information; experimental part, p. 8492 - 8495 (2009/05/11)
(Chemical Equation Presented) Enamides made easy: A catalyst system generated in situ using bis(2-methallyl)-(cycloocta-1,5-diene)ruthenium(II), 1,4-bis(dicyclohexylphosphino)butane, and ytterbium triflate efficiently catalyzes the addition of primary amides to terminal alkynes, selectively forming the Z-anti-Markovnikov enamides. The E isomers are also accessible by combining the hydroamidation with an in situ double-bond isomerization reaction.
