Convenient and Practical Alkynylation of Heteronucleophiles with Copper Acetylides

Cédric Theunissen; Morgan Lecomte; Kévin Jouvin; Anouar Laouiti; Céline Guissart; Jérémy Heimburger; Estelle Loire; Gwilherm Evano

doi:10.1055/s-0033-1341025

Synthesis, Inhaltsverzeichnis

Synthesis 2014; 46(09): 1157-1166
DOI: 10.1055/s-0033-1341025

practical synthetic procedures

Convenient and Practical Alkynylation of Heteronucleophiles with Copper Acetylides

Cédric Theunissen

^aLaboratoire 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

^aLaboratoire 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

^bInstitut Lavoisier de Versailles, UMR CNRS 8180, Université de Versailles Saint-Quentin en Yvelines, 45 Avenue des Etats-Unis, 78035 Versailles Cedex, France

,

Anouar Laouiti

^bInstitut Lavoisier de Versailles, UMR CNRS 8180, Université de Versailles Saint-Quentin en Yvelines, 45 Avenue des Etats-Unis, 78035 Versailles Cedex, France

^cLaboratoire 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: gevano@ulb.ac.be

,

Céline Guissart

^aLaboratoire 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

^bInstitut Lavoisier de Versailles, UMR CNRS 8180, Université de Versailles Saint-Quentin en Yvelines, 45 Avenue des Etats-Unis, 78035 Versailles Cedex, France

,

Estelle Loire

^bInstitut Lavoisier de Versailles, UMR CNRS 8180, Université de Versailles Saint-Quentin en Yvelines, 45 Avenue des Etats-Unis, 78035 Versailles Cedex, France

,

Gwilherm Evano*

^aLaboratoire de Chimie Organique, Service de Chimie et PhysicoChimie Organiques, Université Libre de Bruxelles, Avenue F. D. Roosevelt 50, CP160/06, 1050 Brussels, Belgium

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Abstract

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

Key words

copper acetylides - alkynylation - ynamides - ynimines - alkynylphosphonates

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Referenzen

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