Rare ginsenosides Rg5 and 20(S)-Rg3 are selectively prepared from PD-type saponins with hydrochloric acid as a catalyst. The effects of acid concentration, ethanol concentration, reaction temperature, and reaction time on the preparation of ginsenoside 20(S)-Rg3 and Rg5 were mainly explored, and the formation mechanism of ginsenoside Rg3 was studied by the isotope labelling method. Results showed that when the concentration of PD-type saponin was 15 mg/mL, the concentration of HCl was 0.02 mol/L, the concentration of ethanol was 99%, the reaction temperature was 60 ℃, and the reaction time was 3.5 h, the yields of 20(S)-Rg3 and Rg5 were 15.32% and 50.12%, respectively, with a de value up to 98.28% for 20(S)-Rg3. The reaction mechanism of the isotope labelling method showed that ginsenoside Rg3 was highly stereoselectively prepared from PD saponin under the catalysis of hydrochloric acid viaan SN2 mechanism. Using this method, 20(S)-Rg3 could be obtained with high stereoselectivity while Rg5 was obtained, which had the advantages of low-cost and easy-to-obtain catalyst, simple operation, etc., and provided a new idea for the one-step synthesis of a variety of high-activity rare ginsenosides.
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