Substitution des halogéno-1 alcynes-1 par les dérivés organométalliques du cuivre. accès à une nouvelle classe de synthons: application à

1-Bromo- and 1-iodo-1-alkynes are alkylated by organocopper(I) compounds. Alkenylcopper(I) derivatives undergo substitution with retention of configuration leading to conjugated and functional enynes, from which conjugated dienes can be obtained.     

Vinly copper reagents-16. Synthesis of conjugated dienes via the addition of vinyl cuprates to acetylene

Some alkenyl cuprates add smoothly to acetylene yielding dienyl cuprates.     

A New Efficient and Stereoselective Synthesis of 1,3E,5Z-Undecatriene

1,3E,5Z-Undecatriene is synthesized by coupling of Z-heptenyl copper reagent, obtained through carbocupration of acetylene, with 1-chloro-1E,3-butadiene, in the presence of 5% NiCl₂(PPh₃)₂     

Organocuivreux vinyliques : III. Carbonatation: Preparation stereospecifique d'acides α-ethyleniques et de quelques derives

Vinylcopper compounds are converted stereospecifically and almost quantitatively to the corresponding β,β-disubstituted α-ethylenic acids by carbonation. The influence of solvants and ligands in this insertion is discussed. Various functional groups are derived from these acids.     

General methodology for the synthesis of conjugated dienic insect sex pheromones

A general methodology for the synthesis of various types of dienic insect sex pheromones (Z-E, E-Z, Z-Z) is based on the carbocupration of acetylene by functionalised or non-functionalised lithium dialkyl cuprates, followed by the coupling of the resulting Z dialkenyl cuprates with functionalised or non-functionalised E or Z alkenyl iodides under Pd° catalysis. The following compounds were efficiently synthesized with a high degree of stereoisomeric purity: (E-Z)7, 9-dodecadien,-l-yl acetate 1 (Lobesia botrana), (E-Z)10, 12-hexadecadien,-l-ol 2 (Bombyx mori), (Z-E)9, 11-tetradecadien,-l-yl acetate 3Spodoptera littoralis), (Z-E)5, 7-dodecadien-l-ol 4 (Malascoma disstria), (Z-Z)11, 13-Hexadecadien-l-al 5 (Amyelois transitella), (Z)9,ll-dodecadien-l-yl acetate 6 (Diparopsis castanea) and (Z-Z)9,11-tridecadien-l-yl acetate 22 (a known “pseudo-pheromone”).     

Diastereoselective allylzincation of γ-oxygenated vinyllithiums bearing functionalized side-chains

Allylzincation of γ-oxygenated vinyllithiums bearing functionalized side-chains proved to be more difficult than that reported in the case of γ-oxygenated vinyllithiums with unfunctionalized side-chains. However, when allylzincation occurs it gives the corresponding linear compounds with high diastereoselection as a consequence of the zinc being coordinated by the two oxygen atoms of the methoxymethyl ether moiety.