Structures of Novel Sesquiterpene Alcohols from<i>Chloranthus japonicus</i>(Chloranthaceae)

Kawabata, Jim; Fukushi, Yukiharu; Tahara, Satoshi; Mizutani, Junya

doi:10.1080/00021369.1984.10866207

Cited by 17 publications

(24 citation statements)

References 8 publications

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“…O n the basis o f FI-M S fragm ents m/z 59 and m/z 223 (M +-5 9 ) (1, 100 and 50% ; 2, 69 and 59% , respectively) due to a 1-hydroxy-1-m ethylethyl side chain, a te tra h y d ro fu ran p art structure for 1 and 2 was suggested. T o prove the proposed structure, 1 was dehydrated w ith PO C l3 to yield 1 a [7], whose exom ethylene were elucidated to be diastereoisom ers having a tetrah y d ro fu ran p a rt structure.N O E betw een the C-10 m ethyl p ro to n s and the C-12 m ethine p ro to n was observed only in 2, while 1 exhibited an N O E betw een C-10 m ethyl and C -1 3 -O H p ro to n s. T his result gave a conclusion th a t 1 and 2 were trans and cis isom ers regarding the sub stitu tio n on the tetra h y d ro fu ran ring, re spectively ( Fig. 1).…”

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Highly Oxygenated Bisabolanoids In Rosa Rugosa Leaves

Hashidoko

Tahara

Iwaya

et al. 1991

Zeitschrift Für Naturforschung C

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Rosa rugosa, Sesquiterpene, Bisabolanoid, ExoperoxideFive novel bisabolane sesquiterpenes possessing a tetrahydrofuran ring or a hydroperoxy group were isolated from Rosa rugosa leaves and their structures elucidated by chemical and spectroscopic methods. These highly oxidized sesquiterpenes were structurally related to bisaborosaol A which is the major bisabolanoid o f the plant. IntroductionSesquiterpenes have rarely been found as co n stituents o f R osaceae plants [1]. H ow ever, Rosa ru gosa T hunb. uniquely contains bisab o lan o id s and carotano id s in the leaves as its m ajo r com p o n en ts [2 -4 ], B isaborosaol A (6), the p red o m in an t bis abolanoid o f R. rugosa [4], has an unm odified isoprene unit on the side chain w hich is possibly oxi dized to yield various m etabolites as F lask am p e t al. (1981) have reported referring to a-bisabolol whose derivatives possessed an oxygenated side chain [5,6], A fu rth er survey o f m ore p o lar sesqui terpenes revealed the presence o f two tetrah y d rofurano (1 and 2) an d three exoperoxy (3 -5) deriv atives o f bisaborosaol A (6) (Fig. 1). In this paper, we describe the isolation and stru ctu ral elucidation o f these new and highly oxygenated b isabolanoids from R. rugosa. T he biological im plication o f these com pounds in the tissues is briefly discussed. Results and DiscussionIn a fu rth er survey o f the co n stitu en ts o f leaf ex tractives, o u r interest was a t first focused upon two substances 1 an d 2 w hich gave a yellow pig m ent on thin layer plates w ith v a n illin -H 2S 0 4 test (R { 0.38 and 0.30 in h e x a n e -E tO A c 3:1, respec tively). By colum n c h ro m ato g rap h y over S i 0 2 gel [4], 1 and 2 were eluted w ith 25% EtO A c/hexane. W ith the guidance o f the co lo ratio n w ith v a n illin -H 2S 0 4 reagent, each co m p o u n d was isolated and fu rth er purified by PT L C successively in h e x a n eEtO Ac 3:1 and C H C l3-M e O H 50:2 to give a colReprint requests to Y. Hashidoko.Verlag der Zeitschrift für N aturforschung, D-7400 Tübingen 0939-5075/91/0500-0357 $01.30/0 orless syrup ( 1 ; 160 mg, and 2 ; 120 mg from 6 kg o f R. rugosa leaves). Both show ed M + 282 in FI-M S and sim ilar 'H N M R spectra to th a t o f 6, suggest ing th at the isolates are diastereoisom ers closely related to 6. Two 3 H singlets in 1 at 8H 1.221 and 1.074 were assignable to C -l3 and C -l4 m ethyl groups, not on an olefinic b ut on an oxygenated aliphatic carbon. F urtherm ore, the detection o f m ethine protons (öH 3.415 in 1 and 3.553 in 2) a t tributable to the oxygenated C -l2 suggested the structural m odification from 6 into a cyclic ether on the side chain.W hen 6 was treated with m -CPBA , two p ro d ucts identical with 1 and 2 were afforded in alm ost equivalent am ount. The l3C N M R spectra dis counted the corresponding epoxy structures be cause o f the chemical shift values o f the oxygenat ed carbon at 8C 86.4 (CH -12), 84.6 (C -8) and 70.1 ( C -l3), for exam ple in 1, whose values were too low to be assigned to epoxy carb...

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Highly Oxygenated Bisabolanoids In Rosa Rugosa Leaves

Hashidoko

Tahara

Iwaya

et al. 1991

Zeitschrift Für Naturforschung C

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“…These data, in addition to the observed 15 carbon signals, which appeared as three quartets, four triplets, six doublets, and two singlets in the DEPT spectrum, suggested the structure of acoradienol. 1) Since the optical rotation, and UV, IR, and CD spectral data of 3 were very similar to those of shizuka-acoradienol (3a) previously isolated from the higher plant Chloranthus japonicus, 12) a similar planar structure could be deduced. The NMR spectral data, however, indicated an upfield shift of the olefinic carbon at C-10 of 3 (d 131.9 instead of 140.1 in 3a) and a downfield shift of C-6 (d 45.6 instead of 31.5 in 3a).…”

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Chemical Constituents of Malagasy Liverworts, Part III: Sesquiterpenoids from Bazzania decrescens and Bazzania madagassa

Harinantenaina

Kurata

Asakawa

2005

CHEMICAL & PHARMACEUTICAL BULLETIN

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The genus Bazzania is one of the most phytochemically studied among the liverworts and has been shown to produce a wide range of sesquiterpenoids and aromatic compounds. The sesquiterpenoids that have been detected are of the aromadendrane, bicyclogermacrene, bazzanene, barbatene, calamenane, cuparane, chamigrene, drimane, pinguisane, myltaylane, and cyclomyltaylane types.1,2) Lignans and bisbibenzyls were also isolated from Bazzania trilobata.3,4) Interestingly, sesquiterpene caffeates, which have been shown to have useful activities such as cytotoxic, antimicrobial, antifungal, and superoxide anion release inhibitory activity have only been found in Bazzania species. 1,2,5) In the course of our ongoing phytochemical studies of the Malagasy liverworts, 6,7) six compounds including a new cuparane-type sesquiterpene (1) were isolated from Bazzania decrescens, while Bazzania madagassa produced a new cyclomyltaylane-type sesquiterpenoid (2) and a new acoradienol: 1S*,4S*,5S*, acora-8(15),9-dien-7R*-ol (3). The biogenesis of the cyclomyltaylane-type sesquiterpenoid is discussed. Results and DiscussionBazzania Decrescens The ether extract of B. decrescens was analyzed with GC/MS and shown to contain a-barbatene (1.7%), cuparene (6%), and bazzanene (41.6%). Silica gel column chromatography of the remaining extract afforded five fractions. Purification on Sephadex LH-20, silica gel, and preparative HPLC of each fraction yielded isobicyclogermacrenal, 8) drimenol and a mixture of drimenyl cis and trans caffeate, 9) which was converted to the trans form on standing at room temperature overnight, 2-methoxy-5-hydroxycuparene (HM-1), 10) and friedelin together with a new cuparane-type sesquiterpenoid (1) (Fig. 1). The structures of the known compounds were determined by comparison of their spectral data with those of authentic samples and reported in the literature.Compound 1 exhibited the molecular formula of C 16 H 24 O 2 as determined using HR-EI-MS. Its IR spectrum showed absorption bands for an hydroxyl group (3328 cm Ϫ1) and aromatic methine strech (3086 cm Ϫ1 ), while the UV spectrum displayed an aromatic ring (206, 272 nm). The 1 H-NMR spectral data (Table 1) , and an upfield methyl signal at d 7.7. The positions of the hydroxyl group at C-2, methyl group at C-3, and methoxyl group at C-4 were determined by careful interpretation of the HMBC spectrum (Fig. 2). Thus the structure of 1 was determined to be 2-hydroxy-4-methoxy-cuparene.Compound HM-1 (4) was previously isolated from the phytopathogenic fungus Helicobasidium mompa, 10) but has not been found in liverworts of the Bazzania genus even though they are known to contain cuparane-type sesquiterpenes as chemical markers. 1)Bazzania Madagassa GC/MS analysis of the ether extract of B. madagassa revealed b-barbatene (5.8%), isobazzanene (9.2%), chamigrene (6.8%), d-cuparene (16.2%), and acora-3,5 diene (1.3%). A combination of column chromatography on Sephadex LH-20, silica gel, and ODS RP-18 of the remaining extract yielded two new compounds (2, 3).Compound 2 exh...

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“…Some species in this genus have long been used as folk medicine for their antitumor, anti-fungal, and anti-inflammatory activities. The natural products described in the literatures as constituents of genus Chloranthus are volatile oil, simple coumarins, amide alkaloids and sesquiterpene lactones with unusual 3,5,6-ring system (Kawabata et al, 1984). It is worth mentioning that Chloranthus plants are chemotaxonomically characteristic due to the presence of typical sesquiterpene lactones having a lindenane skeleton named shizukanolides and chloranthalactones (Kawabata et al, 1979 andUchida et al, 1980;Tahara et al, 1981).…”

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Lignan constituents from Chloranthus japonicus Sieb.

et al. 2009

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A new coumarinolignan glucoside named yinxiancaoside C, along with five known benzofuran lignans, have been isolated from the whole plant of Chloranthus japonicus Sieb. The structures of compounds 1-6 were elucidated by chemical and spectroscopic methods including 1D-NMR, 2D-NMR, ESI-MS and HR-ESI-MS. Five known benzofuran lignans were firstly discovered in the Chloranthaceae. In addition, the cytotoxic activity of the isolated compounds against human hepatoma (Hepg-2), ovarian carcinoma (OV420), and breast cancer (MCF-7) cells was investigated by MTT method.

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Structures of Novel Sesquiterpene Alcohols fromChloranthus japonicus(Chloranthaceae)

Cited by 17 publications

References 8 publications

Highly Oxygenated Bisabolanoids In Rosa Rugosa Leaves

Highly Oxygenated Bisabolanoids In Rosa Rugosa Leaves

Chemical Constituents of Malagasy Liverworts, Part III: Sesquiterpenoids from Bazzania decrescens and Bazzania madagassa

Lignan constituents from Chloranthus japonicus Sieb.

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