Synthesis 2014; 46(09): 1157-1166
DOI: 10.1055/s-0033-1341025
practical synthetic procedures
© Georg Thieme Verlag Stuttgart · New York

Convenient and Practical Alkynylation of Heteronucleophiles with Copper Acetylides

Cédric Theunissen
a  Laboratoire de Chimie Organique, Service de Chimie et PhysicoChimie Organiques, Université Libre de Bruxelles, Avenue F. D. Roosevelt 50, CP160/06, 1050 Brussels, Belgium
,
Morgan Lecomte
a  Laboratoire de Chimie Organique, Service de Chimie et PhysicoChimie Organiques, Université Libre de Bruxelles, Avenue F. D. Roosevelt 50, CP160/06, 1050 Brussels, Belgium
,
Kévin Jouvin
b  Institut Lavoisier de Versailles, UMR CNRS 8180, Université de Versailles Saint-Quentin en Yvelines, 45 Avenue des Etats-Unis, 78035 Versailles Cedex, France
,
Anouar Laouiti
b  Institut Lavoisier de Versailles, UMR CNRS 8180, Université de Versailles Saint-Quentin en Yvelines, 45 Avenue des Etats-Unis, 78035 Versailles Cedex, France
c  Laboratoire de Chimie Hétérocyclique, Produits Naturels et Réactivité, Département de Chimie, Faculté des Sciences de Monastir, Université de Monastir, Avenue de l’environnement, 5019 Monastir, Tunisia   Fax: +32(2)6502798   Email: [email protected]
,
Céline Guissart
a  Laboratoire de Chimie Organique, Service de Chimie et PhysicoChimie Organiques, Université Libre de Bruxelles, Avenue F. D. Roosevelt 50, CP160/06, 1050 Brussels, Belgium
,
Jérémy Heimburger
b  Institut Lavoisier de Versailles, UMR CNRS 8180, Université de Versailles Saint-Quentin en Yvelines, 45 Avenue des Etats-Unis, 78035 Versailles Cedex, France
,
Estelle Loire
b  Institut Lavoisier de Versailles, UMR CNRS 8180, Université de Versailles Saint-Quentin en Yvelines, 45 Avenue des Etats-Unis, 78035 Versailles Cedex, France
,
Gwilherm Evano*
a  Laboratoire de Chimie Organique, Service de Chimie et PhysicoChimie Organiques, Université Libre de Bruxelles, Avenue F. D. Roosevelt 50, CP160/06, 1050 Brussels, Belgium
› Author Affiliations
Further Information

Publication History

Received: 17 February 2014

Accepted after revision: 25 February 2014

Publication Date:
25 March 2014 (online)


Dedicated to Prof. François Couty on the occasion of his 50th birthday

Abstract

Copper acetylides, readily available reagents which are characterized by their lack of reactivity, can be simply activated by oxidation with oxygen in the presence of simple nitrogen ligands such as TMEDA or imidazole derivatives. Upon activation, these nucleophilic species undergo a formal umpolung and can transfer their alkyne subunit to a wide range of heteronucleophiles, including amides, oxazolidinones, imines, and dialkyl phosphites. This alkynylation, which provides one of the most practical entry to useful building blocks such as ynamides, ynimines, and alkynylphosphonates, proceeds under especially mild conditions and can be easily performed on a multigram scale.

Supporting Information

 
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