The selective aerobic oxidation of alkynes to corresponding α,β-acetylenic ketones was achieved in polyethylene glycol/dense CO2/O2 biphasic system without any catalyst or additive. The effects of reaction parameters, e.g. temperature, CO2 pressure, PEG molecular weight and loading on the reaction were carefully examined. Moreover, various substrates worked well in the presence of PEG 1000 under 5 MPa of CO2 and 2 MPa of O2 at 100 ℃ for 12 to 24 h and acceptable yield and selectivity could be obtained in most cases. Preliminary mechanistic investigations were also discussed.
