par Guissart, Céline 
;Luhmer, Michel ;Evano, Gwilherm
Référence Tetrahedron, 74, page (6727-6736)
Publication Publié, 2018
;Luhmer, Michel ;Evano, Gwilherm Référence Tetrahedron, 74, page (6727-6736)
Publication Publié, 2018
Article révisé par les pairs
| Résumé : | Copper acetylides are readily available and especially convenient reagents for the alkynylation of a broad range of heteronucleophiles. Upon simple activation with molecular oxygen in the presence of suitable ligands and solvents, they readily transfer their alkyne moiety at room temperature, notably yielding a variety of nitrogen- and phosphorus- substituted alkynes. We report in this manuscript an extensive study of the chemoselectivity of this alkynylation based on quantitative 13C NMR analyses. With suitable ligand/solvent combinations, various phosphorus-based nucleophiles can be alkynylated with excellent levels of selectivity, even in the presence of a large excess of nitrogen-nucleophiles. This chemoselective alkynylation could be further extended to an even more challenging selective alkynylation of a nitrogen-nucleophile over another one, further highlighting the synthetic potential of copper acetylides as alkynylating agents that can selectively “fish” a nucleophile without affecting others. |
