Structural Revision of Terpenoids with a (3Z)-2-Methyl-3-penten-2-ol Moiety by the Synthesis of (23E)- and (23Z)-Cycloart-23-ene-3β,25-diols

Takahashi, Shigetoshi; Satoh, Hiroko; Hongo, Yayoi; Koshino, Hiroyuki

doi:10.1021/jo070478m

Cited by 30 publications

(45 citation statements)

References 32 publications

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“…The high resolution-electronspray ionization-mass spectra (HR-ESI-MS) displayed a molecular ion peak at m/z 441. 4100 4) Compared with the reported data, 2,4) the stereochemistry of the double bond should be E. The structure of 1 was further confirmed by the single-crystal X-ray diffraction (Fig. 1).…”

Section: )mentioning

confidence: 70%

“…1) It has not been chemically studied previously. In our current study, four new compounds (1, 2, 6, 7) and three known compounds (3)(4)(5) were isolated from aerial parts of Aphanamixis grandifolia collected from Hainan Province, People's Republic of China. The structures of the new compounds were characterized using spectroscopic methods, and the structure of compound 1 was confirmed by single-crystal X-ray diffraction analysis.…”

Section: Regular Articlementioning

confidence: 94%

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Chemical Constituents from Aphanamixis grandifolia

Liu

Chen

Shi

et al. 2010

CHEMICAL & PHARMACEUTICAL BULLETIN

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The genus Aphanamixis (Meliaceae) comprising about 5 species and varieties is mainly distributed in China, India and Indonesia. Aphanamixis grandifolia, an arbor tree mainly growing in southern China, is a medicinal plant employed as an astringent for spleen, liver, tumors, abdominal diseases, and applied in treatment of rheumatism in southeast Asia. 1)It has not been chemically studied previously. In our current study, four new compounds (1, 2, 6, 7) and three known compounds (3-5) were isolated from aerial parts of Aphanamixis grandifolia collected from Hainan Province, People's Republic of China. The structures of the new compounds were characterized using spectroscopic methods, and the structure of compound 1 was confirmed by single-crystal X-ray diffraction analysis. The known compounds were elucidated by comparing their spectroscopic data with those reported in the literature. Their structures were identified as (23E)-25-methylcycloart-23-en-3b-ol (1), a novel triterpenoid possessing a C 31 skeleton, (17E)-cycloart-17,26-dien3b-ol (2), (23E)-cycloart-23-en-3b,25-diol (3), 2) (23E)-25-methoxycycloart-23-en-3b-ol (4), 2) cycloart-3b,25-diol (5), 3) 4R-hydroxy-4-(9S-hydroxy-12-methylhexan-6-yl)-3-methylcyclopent-2-enone (6), and 7-hydroxy-5-(2Ј-hydroxy-4Ј,5Ј-dimethoxyphenyl)-2-methoxy-6-methyl-1,4-naphthoquinone (7). In addition, the cytotoxicities of the compounds were evaluated against selected cancer cell lines, including human leukaemia cell (HL-60), human hepatoma cell (Hep G2), and human cervical carcinoma cell (HeLa) lines. The compound 3 was active (HL60 cell, IC 50 ϭ5.97 mg/ml; Hep G2, IC 50 ϭ 20.85 mg/ml; HeLa, IC 50 ϭ24.89 mg/ml), compounds 1, 2, 5, 6 and 7 exhibited modest cytotoxicities. Herein we report the isolation, structural elucidation, and biological activities of these compounds. Results and DiscussionThe ethanolic extract of the aerial parts of Aphanamixis grandifolia was concentrated under vacuum and then subjected repeatedly to column chromatography over silica gel, Sephadex LH-20, and MCI yield compounds 1-7 (Chart 1).The 1 H-NMR spectra of compounds 1-5 indicated the presence of a cycloartane skeleton with 3b-ol group on C-3.2)This fact was evidenced by the typical H-19 doublets at d H 0.33 (Jϭ3.9 Hz) and 0.55 (Jϭ3.9 Hz), and the oxygenated methine near at d H 3.30 (m). Comparison of the 13 C-NMR spectra of 1-5 with those of related cycloart-3b-ol compounds in the literature, 2) the methylene of C-19 at d C 30.0 and the methine of C-3 at d C 78.8, confirmed that these were all 3b-hydroxycycloartanes.Compound 1 was obtained as a colorless crystal. The high resolution-electronspray ionization-mass spectra (HR-ESI-MS) displayed a molecular ion peak at m/z 441.4100 [Mϩ H] ϩ (Calcd for C 31 H 53 O, 441.4096) consistent with a molecular formula of C 31 H 52 O, requiring seven degrees of unsaturation, which was confirmed by 13 C-NMR and distortionless enhancement by polarization transfer (DEPT) analysis. The 13 C-NMR spectrum indicated 31 resonances ascribed to seven tertiary methyl, one...

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Section: )mentioning

confidence: 70%

Section: Regular Articlementioning

confidence: 94%

Chemical Constituents from Aphanamixis grandifolia

Liu

Chen

Shi

et al. 2010

CHEMICAL & PHARMACEUTICAL BULLETIN

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“…The signals related to the olefinic protons resulted in a multiplet at δH 5.6 that could not be resolved by obtaining a spectrum of 2 in other deuterated solvents, precluding the straightforward assignment of the geometry of the double bond based on the magnitude of the vicinal coupling constant value. Accordingly, the geometry of the side chain was established as E primarily based on comparison of the 13 C NMR spectroscopic data of analogues with similar side chain [52][53][54] and further backed up by biosynthetic considerations since most related triterpenes isolated from plants display this configuration [55]. Altogether, these data led to characterize the 2D structure of 2 as displayed in Fig.…”

Section: Figure 2 Tablementioning

confidence: 99%

Further terpenoids from Euphorbia tirucalli

et al. 2019

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The phytochemical investigation of Euphorbia tirucalli L. (Euphorbiaceae) yielded four new compounds, including a rare cadalene-type sesquiterpene (tirucadalenone), two tirucallane triterpenoids, euphorol L and euphorol M, with the latter being described as an epimeric mixture, and a euphane triterpene, namely, euphorol N, together with 7 known compounds. Their structures and absolute configurations were elucidated from analysis of 1D (1H, J-modulated 13 C) and 2D NMR (HSQC, HMBC and NOESY), high-resolution mass spectrometry (HRESIMS), optical rotation, and GIAO NMR shift calculation followed by CP3 analysis, along with comparison with literature reports. All these compounds were tested for cytotoxicity against K562, MCF-7 and/or and HepG2 tumor cell lines. Only tirucadalenone displayed a mild cytotoxic activity. Graphical abstractFour previously undescribed terpenoids: a cadalene (1), two tirucallanes (2 and 3a/3b), and a euphane (4) were isolated from Euphorbia tirucalli L. ACCEPTED MANUSCRIPT

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“…Moreover, NOE correlations were observed between H-8 with H-13 but not with H 3 -14, and between H-7 with H 3 -14, indicating that H 3 -14 has a β-orientation. Furthermore, the configuration of the double bond at C-16/C-17 was determined by comparison of the NMR data of 1 in CDCl 3 with those of two related synthetic compounds, (23 E )-cycloart-23-ene-3β,25-diol ( 4 ) and (23 E )-cycloart-23-ene-3β,25-diol ( 5 ) (Figure 4), also measured in CDCl 3 (Table 2) [16]. Comparison of the NMR data of 1 and 4 confirmed that both compounds have the same partial structure from C-15 to C-20 of 1 and from C-22 to C-27 of 4 .…”

Section: Resultsmentioning

confidence: 99%

A New Spatane Diterpenoid from the Cultured Soft Coral Sinularia leptoclados

Tsai¹,

et al. 2013

Marine Drugs

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A new spatane diterpenoid, leptoclalin A (1), along with two previously reported known norcembranoid diterpenes (2 and 3), were isolated from a cultured soft coral Sinularia leptoclados. The structures were determined by extensive spectroscopic analyses and by comparison with the spectral data of related known compounds. Metabolite 1 is rarely found in spatane skeletons reported from soft corals. In addition, compound 1 exhibited weak cytotoxicity towards human tumor cell lines T-47 D and K-562.

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Structural Revision of Terpenoids with a (3Z)-2-Methyl-3-penten-2-ol Moiety by the Synthesis of (23E)- and (23Z)-Cycloart-23-ene-3β,25-diols

Cited by 30 publications

References 32 publications

Chemical Constituents from Aphanamixis grandifolia

Chemical Constituents from Aphanamixis grandifolia

Further terpenoids from Euphorbia tirucalli

A New Spatane Diterpenoid from the Cultured Soft Coral Sinularia leptoclados

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