Regio- and stereo-selective hydroxylations of ingenane diterpenoids by Mortierella ramanniana and Gibberella fujikuroi / 中国天然药物

The regio- and stereo-selective hydroxylations of two ingenane diterpenoids, 20-deoxyingenol (1) and 13-oxyingenol dodecanoat (2), by the filamentous fungi Mortierella ramanniana and Gibberella fujikuroi were investigated in the present study. Four undescribed metabolites (3-6) of substrate 1 and two undescribed metabolites (7 and 8) of substrate 2 were isolated. All the metabolites were identified as hydroxylated ingenane derivatives by extensive NMR and HR-ESI-MS data analyses. All the biotransformed compounds and the substrates were evaluated for their cytotoxicities against three human cancer cell lines, including human colon cancer Caco-2, breast cancer MCF-7, and adriamycin (ADM)-resistant MCF-7/ADM cell lines. All ingenane alcohols (1, and 3-6) displayed no significant cytotoxic activities. The substrate 13-oxyingenol dodecanoat (2) showed moderate cytotoxicity with IC values being 35.59 ± 5.37 μmol·L (Caco-2), 24.04 ± 4.70 μmol·L (MCF-7), and 22.24 ± 5.19 μmol·L (MCF-7/ADM). However, metabolites 7 and 8 displayed no significant cytotoxicity. These results indicated that the hydroxylation at the C-13 aliphatic acid ester of substrate 2 can significantly reduce the cytotoxic activity.

Ingenane diterpene ester constituents from Tibetan medicine Euphorbia wallichii / 中草药

Objective To study the chemical constituents from the acetone extract in the root of Tibetan medicine Euphorbia wallichii. Methods The constituents were separated by column chromatography with silica gel and purified by Sephadex LH-20. Their structures were identified on the basis of spectral analysis such as IR, HRESIMS, HRSIMS, and 1D-and 2D-NMR techniques ( 1H- 1H COSY , HMQC, HMBC). Results Six compounds were isolated from the acetone extract in the root of E. wallichii. Their structures were identified as lanosterol (Ⅰ), ingenol-20-myristinate (Ⅱ), ingenol-3-myristinate (Ⅲ), acid (Ⅳ), 1-O-?-L-arabinofuranosyl-(1→6)-?-D-glucopyranosyl-3, 7-dimethyl-oct-2-en-7-ol (Ⅴ), 1-O-galloyl-?-D-glucose (Ⅵ) . Conclusion Ingenane diterpene esters ingenol-20-myristinate (Ⅱ) and ingenol-3-myristinate (Ⅲ) are new compounds and other compounds are found from this plant for the first time. It is the first time that monoterpene disaccharide glycoside, compound Ⅴ, is isolated from the plants of Euphorbia L.