Eight new diterpenoids and two new nor-diterpenoids from the stems of Croton cascarilloides.
From the stems of Croton cascarilloides, eight new diterpenoids, named crotocascarins A-H (1-8), having a crotofolane skeleton were isolated along with two new nor-diterpenoids (9 and 10), named crotocascarins α and β, derived through rearrangement of the crotofolane skeleton. The structures of these compounds were elucidated by means of extensive one- and two-dimensional NMR spectroscopic analyses. The absolute structures of the diterpene moiety were determined by application of the circular dichroism (CD) rule for the γ-lactone ring. The relative structures of the two crotofolanes (1 and 2) and one rearranged compound (9) were confirmed by X-ray crystallographic analyses. Compounds 1, 2 and 9 possessed 2-methylbutyric acid in their molecules, the absolute configuration of which was found to be 2S by comparison of its HPLC behavior with that of an authentic sample. Therefore, the absolute structures of these crotocascarins (1, 2 and 9) were unambiguously determined. The absolute structures of crotofolanes are reported for the first time in this paper.
Graduate School of Biomedical and Health Sciences, Hiroshima University, 1–2–3 Kasumi, Minami-ku, Hiroshima, Japan.
Susumu
S
Kawakami
Hiroki
H
Toyoda
Liva
L
Harinantenaina
Katsuyoshi
K
Matsunami
Hideaki
H
Otsuka
Takakazu
T
Shinzato
Yoshio
Y
Takeda
Masatoshi
M
Kawahata
Kentaro
K
Yamaguchi
D002942:Circular Dichroism; D029802:Croton / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004224:Diterpenes / Q000737:chemistry / Q000302:isolation & purification; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D018547:Plant Stems / Q000737:chemistry; D013237:Stereoisomerism
D004224:Diterpenes