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Two new spirostanol saponins, kingianoside I 1 and kingianoside K 2, corresponding to 3β,23S,25R23hydroxy12oxospirost5en3yl 4OβDglucopyranosylβDgalactopyranoside 1 and 3β,25R7oxospirost5en3yl αLarabinofuranosyl1→46deoxyαLmannopyranosyl1→2βDglucopyranoside 2, along with 13 known compounds, daucosterol, 25Rkingianoside G, 25RSkingianoside A, pratioside D1, 25RSpratioside D1, 25Skingianoside C, kingianoside C, ginsenoside Rb1, saponins Tb and Pb, dioscin, gracillin, and saponin Pa, were isolated from the processed rhizomes of Polygonatum kingianum.The structures of the new compounds were elucidated by detailed spectroscopic analyses, including 1D and 2DNMR techniques, and chemical methods. Compound 2contains a novel unusual spirostanol saponin aglycone. Ginsenoside Rb1and saponin Tb were isolated for the first time from the genus Polygonatum.The 13 known compounds were detected for the first time in the processed Polygonatum kingianum. [ABSTRACT FROM AUTHOR]