Methyl (S)-beta-hydroxybutyrate, the important chiral building block for organic synthesis was produced in high yield from the methoxycarbonylation of (S)-propylene oxide ((S)-PO) using a catalytic system consisting of dicobalt octacarbonyl [CO2(CO)(8)] and pyrazole. The effects of different additives, temperature and CO pressure were investigated. The reaction was greatly influenced by the variation of temperature, both the conversion of (S)-PO and the selectivity of methyl (S)-beta-hydroxybutyrate decreased with increasing temperature (above 80 degrees C). Nevertheless, the enantiomeric excess (ee) of methyl (S)-beta-hydroxybutyrate is independent of the parameter of reaction temperature, no racemization reaction takes place even the reaction temperature reaches 150 degrees C. A possible process for the formation of ethers and diethers was presented. The reaction has a bright future in an industrial scale. (c) 2007 Elsevier B.V. All rights reserved.