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

Huan-Feng Jiang; Jin-Yu Tang; A.-Zhong Wang; Guo-Hua Deng; Shao-Rong Yang

doi:10.1055/s-2006-926372

PAPER

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

Huan-Feng Jiang*^a, Jin-Yu Tang^b,c, A-Zhong Wang^a, Guo-Hua Deng^a, Shao-Rong Yang^a
^a College of Chemistry, South China University of Technology, Guangzhou, 510640, China
Fax: +86(20)87112906; e-Mail: jianghf@scut.edu.cn;
^b Guangzhou Institute of Chemistry, Chinese Academy of Sciences, Guangzhou 510650, China
^c Graduate School, Chinese Academy of Sciences, Beijing 100039, China

Abstract

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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.

Key words

Cu(II)-promoted - homocoupling reaction - alkynes - supercritical carbon dioxide

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