Ocotillol, pseudo-ginsenoside RT5 (RT
5), and pseudo-ginsenoside F
11 (PF
11) are ocotillol-type saponins that have the same aglycone structure but with different numbers of glucose at the C-6 position. In this study, the metabolites of ocotillol, RT
5, and PF
11 in rat plasma, stomach, intestine, urine, and feces after oral administration were investigated by ultra-performance liquid chromatography coupled with time-of-flight mass spectrometry. The results showed that RT
5 was easily biotransformed into metabolites
in vivo, whereas PF
11 and RT
5 were difficult to be biotransformed. Hydrogenation, dehydrogenation, dehydration, deglycosylation, deoxygenation, hydration, phosphorylation, deoxidation, glucuronidation, and reactions combining amino acid were speculated to be involved in the biotransformation of ocotillol, RT
5, and PF
11. Based on the structural analysis of metabolites, it was deduced that hydrogenation, dehydration, deoxidation, and reactions combining amino acid occurred on the aglycone structure, whereas deglycosylation, hydration, and phosphorylation occurred on the glycosyl chain. Further, metabolites in plasma, urine, feces, and tissues were different: First, glucuronidation products were found in urine, stomach, intestine, and feces, but not in plasma. Second, the ocotillol prototype was not identified in urine samples. Third, the RT
5 prototype was found in stomach, intestine, feces, and urine, but not in plasma.
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