From the 1-BuOH-soluble fraction of a methanol (MeOH) extract of the leaves of Croton cascarilloides, crotofolanes: crotocascarins I-K, nor-crotofolane: crotocascarin γ, isocrotofolane glucoside and phenolic glycoside were isolated by a combination of various separation techniques. Their structures were elucidated mainly from the NMR spectroscopic evidence. The structure of crotocascarin K was first elucidated by spectroscopic analysis and then was confirmed by X-ray crystallographic analysis. Its absolute structure was finally determined by the modified Mosher's method. Isocrotofolane glucoside was found to possess a new skeleton, however, its absolute structure remains to be determined.Key words Croton cascarilloides; Euphorbiaceae; crotocascarin; crotofolane; nor-crotofolane; isocrotofolane A diterpenoid, phorbol 12-myristate 13-acetate, isolated from Croton oil is known to have a potent tumor-promoting effect 1,2) and is often employed in biomedical research to activate protein kinase C.3) Thus, Croton species plants attracted our attention. C. cascarilloides RÄUSCHEL is an evergreen shrubby tree that grows on elevated coral reefs of the Okinawa Islands, Taiwan, southern China, the Malay Peninsula and Malaysia. The leaves are oblong-lanceolate to oblong-oval, and their undersurface is covered by shiny white ramenta.4) In a previous study, 5) investigation of the constituents of the stems of Croton cascarilloides provided eight rare crotofolane-type and two rearranged crotofolane-type diterpenoids. In this study, from the 1-BuOH-soluble fraction of a MeOH extract of the leaves of C. cascarilloides, three crotofolane-type diterpenoids, named crotocascarins I-K (1-3), a nor-diterpenoid, crotocascarin γ (4), a diterpenoid glucoside with a new skeleton, which was named isocrotofolane glucoside (5), and one phenolic glycoside (6) along with two known compounds (7, 8) were isolated. The structures of the new compounds isolated were elucidated from spectroscopic evidence and that of crotocascarin K (3) was determined by X-ray crystallographic analysis, followed by application of the modified Mosher's method to clarify its absolute structure. The known compounds were identified as angelicoidenol 2-O-β-D-glucopyranoside (7) 6) and senecrassidiol (8) 7) by comparison of the physico-chemical data with those reported in the literature.
Results and DiscussionFrom the 1-(butanol) BuOH-soluble fraction of a MeOH extract of the leaves of C. cascarilloides, three crotofolane-type diterpenoids, named crotocascarins I-K (1-3), a nor-diterpenoid, crotocascarin γ (4), a diterpenoid glucoside with a new skeleton, which was named isocrotofolane glucoside (5), and a phenolic glycoside (6) H-NMR spectrum, signals for one singlet methyl at δ H 1.05, two doublet methyls at δ H 1.02 (J=7.2 Hz) and 1.91 (J=1.2 Hz), and two olefinic protons at δ H 5.06 (1H, s) and 5.07 (1H, s) were observed. The 13 C-NMR spectrum together with distortionless enhancement polarization transfer (DEPT) results revealed a total of 20 resonances, which compris...