An unprecedented highly efficient solvent-free oxidation of alkynes to alpha,beta-acetylenic ketones with tert-butyl hydroperoxide catalyzed by water-soluble copper complex

作者：Ajjou Abdelaziz Nait^*; Ferguson Gabriel

来源：Tetrahedron Letters, 2006, 47(22): 3719-3722.

DOI：10.1016/j.tetlet.2006.03.140

• oxidation
• water-soluble catalyst
• copper chloride
• tert-butyl hydroperoxide
• alkynes
• alpha,beta-acetylenic ketone

The catalytic system composed of CuCl2 and 2,2'-biquinoline-4,4'-dicarboxylic acid dipotassium salt (BQC) was found to be highly efficient for the selective alpha-oxidation of internal alkynes to the corresponding alpha,beta-acetylenic ketones, with aqueous tert-butyl hydroperoxide under mild conditions. For the first time, full conversions of alkynes were reached with excellent selectivities. and propargylic tert-butylperoxy ethers were observed and suggested as the reaction intermediates. In the case of terminal alkynes. the oxidations are sluggish and low yields ranging front 32% to 40%, were obtained.

• 出版日期2006-5-29