0000000000732801
AUTHOR
Andre Job
Copper(I) Iodide Polyphosphine Adducts at Low Loading for Sonogashira Alkynylation of Demanding Halide Substrates: Ligand Exchange Study between Copper and Palladium
The prestabilization of copper iodide with a multidentate ferrocenyl phosphine ligand promotes the palladium-catalyzed cross-coupling of demanding halides with phenylacetylene in a selective way. Novel CuI-triphosphine adducts are described in the solid state and in solution. Their use allowed the introduction of the copper iodide cocatalyst in unprecedented low amounts (0.4 to 0.1 mol %) in systems also employing low amounts of “ligand-free” [PdII(η3-allyl)Cl]2 precursor (0.2 to 0.05 mol %). The scope of substrates is reported, and electronically or sterically deactivated bromides were efficiently coupled. Concerning aryl chlorides, electron-poor activated substrates were also coupled usin…
Uncommon perspectives in palladium- and copper-catalysed arylation and heteroarylation of terminal alkynes following Heck or Sonogashira protocols: Interactions copper/ligand, formation of diynes, reaction and processes in ionic liquids
Abstract Conjugated alkynes are recurring building blocks in natural products and in a wide range of important compounds, such as pharmaceuticals, agrochemicals, or molecular materials. The palladium-catalysed cross-coupling reaction between the sp 2 -hybridized carbon atoms of aryl, heteroaryl, and vinyl halides with the sp -hybridized carbon atoms of terminal alkynes is one of the most important developments in the field of alkyne chemistry over the past 50 years. Room for improvement still exists in these important reactions of direct arylation of terminal alkynes. In this prospect, the present authors have developed several strategies aiming at improving the reactivity, the selectivity,…