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Synthesis 2009(13): 2283-2288  
DOI: 10.1055/s-0029-1216847
PSP
© Georg Thieme Verlag Stuttgart ˙ New York

Ruthenium-Catalyzed Addition of Primary Amides to Alkynes: A Stereoselective Synthesis of Secondary Enamides

Lukas J. Gooßen*, Mathieu Blanchot, Kifah S. M. Salih, Käthe Gooßen
Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Straße 54, 67663 Kaiserslautern, Germany
Fax: +49(631)3921; e-Mail: goossen@chemie.uni-kl.de;
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Publikationsverlauf

Received 13 March 2009
Publikationsdatum:
29. Mai 2009 (online)

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Abstract

The anti-Markovnikov addition of primary amides to terminal alkynes under the formation of Z-configured secondary enamides is efficiently promoted by a catalyst system generated in situ from bis(2-methallyl)(cycloocta-1,5-diene)ruthenium(II), 1,4-bis(dicyclohexylphosphino)butane, and ytterbium triflate. The thermodynamically more stable E-isomers are accessible by combining the above hydro­amidation with an in situ double-bond isomerization reaction, using triethylamine and molecular sieves.

Key words

alkynes - amides - enamides - hydroamidation - ruthenium

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