Cu(II)-Promoted Oxidative Homocoupling Reaction of Terminal Alkynes in Supercritical Carbon Dioxide

 

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Abstract

Oxidative homocoupling reaction of various terminal alkynes in supercritical carbon dioxide (scCO₂) has been reported. The final optimized reaction conditions for the reaction in scCO₂ were determined to be cupric chloride (2 mmol), sodium acetate (2 mmol), methanol (1 mL) and CO₂ (14 MPa) at 40 °C. Sodium acetate was superior to pyridine in the present reaction system. Methanol, as a co-solvent of scCO₂, was necessary to help dissolve the inorganic salt and facilitated the reaction. Higher solubility of cupric chloride in the scCO₂-methanol medium than other cupric salts, e.g. CuSO₄, Cu(NO₃)₂, Cu(OAc)₂ and cupric bromide, guaranteed its high catalytic ability. Variations of the pressure of scCO₂ and temperature in a certain range have almost little impact on the reaction efficiency. A mechanism involving copper(II)-acetylide complex was supposed in which AcO^- or Cl^- instead of N-containing compounds acted as ligands. The reaction system in scCO₂ is an effective and environmental-friendly alternative to the previous methods of homocoupling of terminal alkynes involving volatile organic compounds.

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