Labdane Diterpenes of Leonurus sibiricus

Boalino, Dionne M.; McLean, Stewart; Reynolds, William F.; Tinto, Winston F.

doi:10.1021/np030480i

Cited by 58 publications

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“…This phenomenon of the co-occurrence of C-15 oxygenated epimeric pairs has been frequently seen in many examples of bis-spirolabdanetype diterpenoids of the genus Leonurus. [2][3][4][5][6][7]9) Although the absolute configurations of 1-12 were not individually confirmed herein, they are probably of the same normal labdane-type diterpenoids on the basis of the co-occurrence with 13 and 14, since the formation of bis-spirotetrahydrofuranes involves only C-9 side chain. Additionally, compounds 1/2 and 4/5 were previously isolated from the same extraction fractions together with 4-b-hydroxymethylpregaleopsin, the absolute assignments of p-bromobenzoate derivative of which have been unambiguously determined by single-crystal X-ray crystallographic analysis.…”

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confidence: 66%

“…8,9) Similarly, two prefuranic labdane-type diterpenoids were isolated from L. heterophyllus collected in Guangdong Province, China.…”

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confidence: 99%

“…Slight differences in (Table 1) and 13 C-NMR (Table 2) spectroscopic data, which contained duplicate resonances of 11/12 and 1/2, suggested that they were stereoisomeric compounds, probably with respect to stereochemistry at C-9 and C-13. In the NOESY spectrum, NOEs were observed between Me-20 [11/12: The finding that 13S and 13R bis-spirolabdane-type diterpenoids co-occurred in the same extract is a rare case in the Leonurus genus, 9) and the lack of any 6-oxygenated function in the 13S series is unique among Leonurus bis-spirocyclic diterpenoids. So far, the Leonurus bis-spirocyclic labdanes clearly differ from analogous compounds from Leonotis and Marrubium 12) by the presence of C-15 oxygenated functions, and from Otostegia 13) and Vitex 14,15) by the presence of 8-acetoxyl and/or C-7-carbonyl groups.…”

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New Bis-spirolabdane-Type Diterpenoids from Leonurus heterophyllus SW.

Giang

Sơn²,

Matsunami

et al. 2005

CHEMICAL & PHARMACEUTICAL BULLETIN

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Leonurus heterophyllus SW. (family: Lamiaceae, syn. Labiatae) is used in Vietnamese traditional medicine for the treatment of menstruation and child delivery in gynaecology, high blood pressure, blood stasis, heart disorders, and dysentery.1) The rich distribution of bis-spirolabdane-type diterpenoids with variations of functionalities in the plants of the genus Leonurus was reported in the previous studies on chemical composition of L. persicus, 2-5) L. cardiaca, 6,7) and L. sibiricus. 8,9) Similarly, two prefuranic labdane-type diterpenoids were isolated from L. heterophyllus collected in Guangdong Province, China.10,11) However, a systematic chemical investigation on L. heterophyllus is necessary for reasons of chemotaxonomic interest. It is noteworthy that bis-spirocyclic labdane-type compounds are not confined to the Leonurus species, and so far have been found in the genera of Leonotis (Lamiaceae), 12) Marrubium (Lamiaceae), 12)Otostegia (Lamiaceae), 13) and Vitex (Verbenaceae). 14,15) In our present study, systematic extraction and isolation afforded twelve natural bis-spirolabdane-type diterpenoids (1-12), eight of which are new (3, 6-12), together with hispanone (13) and galeopsin (14). The known diterpenoids, leopersin B (1), 15-epileopersin B (2), leopersin C (4), 15-epileopersin C (5), 13 and 14 are identified on the basis of physical ([a] D ), and 1 H-and 13 C-NMR data. 2,3,16,17) Air-dried aerial parts of L. heterophyllus were extracted with MeOH by percolation at room temperature. Concentration under reduced pressure yielded an extract, which was divided into n-hexane-, ethyl acetate-and 1-BuOH-soluble parts by sequential solvent partitioning with H 2 O. Bis-spirocyclic compounds 1-12, and compounds 13 and 14 were obtained by systematic fractionation of n-hexane-soluble fraction first over silica gel, then over reversed-phase octadecyl silica (ODS) gel, followed by preparative HPLC. While compounds 3, 8, 13 and 14 were obtained in pure form, the other compounds were isolated as epimeric pairs 1/2, 4/5, 6/7, 9/10 and 11/12 at C-15 position. This phenomenon of the co-occurrence of C-15 oxygenated epimeric pairs has been frequently seen in many examples of bis-spirolabdanetype diterpenoids of the genus Leonurus. [2][3][4][5][6][7]9) Although the absolute configurations of 1-12 were not individually confirmed herein, they are probably of the same normal labdane-type diterpenoids on the basis of the co-occurrence with 13 and 14, since the formation of bis-spirotetrahydrofuranes involves only C-9 side chain. Additionally, compounds 1/2 and 4/5 were previously isolated from the same extraction fractions together with 4-b-hydroxymethylpregaleopsin, the absolute assignments of p-bromobenzoate derivative of which have been unambiguously determined by single-crystal X-ray crystallographic analysis.2) Therefore, the stereochemistry of 1-12 is suggested to be presented as in the normal series of labdane-type diterpenoids.Leoheteronone A (3) , including eight new, named leoheteronones A-E (3, 6, 8, 9, 11), 15-...

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confidence: 66%

“…8,9) Similarly, two prefuranic labdane-type diterpenoids were isolated from L. heterophyllus collected in Guangdong Province, China.…”

mentioning

confidence: 99%

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confidence: 99%

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New Bis-spirolabdane-Type Diterpenoids from Leonurus heterophyllus SW.

Giang

Sơn²,

Matsunami

et al. 2005

CHEMICAL & PHARMACEUTICAL BULLETIN

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“…Alkaloids (Murakami 1943), terpenoids (Savona et al 1982;Boalino et al 2004;Almeida et al 2005) and furanolactones (Satoh et al 2003) have been isolated from the plant, together with rutin and its derivatives and methoxylated flavones (Almeida et al 2006). These latter compounds seem to be important chemotaxonomic markers in the genus Leonurus (Giang et al 2005).…”

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In vitroallelopathic potential ofLeonurus sibiricusL. leaves

Almeida

Delachiave

Sannomiya

et al. 2008

Journal of Plant Interactions

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The chemical interaction between plants is known as allelopathy and it is related to the release of substances into the environment. The present study aimed at the evaluation of the allelopathic activity of the leaves of Leonurus sibiricus against the germination and initial growth of Raphanus sativus, Lactuca sativa, and Lepidium sativum. Chemical analyses showed the presence in the leaves of four major flavonoids (quercetin-3-O-a-L-rhamnopyranosyl-(1 6)-b-D-galactopyranoside; rutin; hyperin, and isoquercetrin) and of three minor flavonoidic compounds (genkwanin, 3?-hydroxy genkwanin, and quercetin). Extracts, their chromatographic fractions and pure isolated flavonoids showed different biological activities. A methanol extract of leaves of Leonurus sibiricus caused significant reduction only in the germination of Lactuca sativa, with no effects on the germinative processes of Raphanus sativus and Lepidium sativum. Some chromatographic fractions, containing the flavonoids, showed inhibitory activity on the initial stages of root growth of all tested seeds. The isolated flavonoids, at the higher concentration tested (10 (4 M) seemed to be responsible for the inhibition of the germination, as well as the radical elongation. Among pure compounds, 3?-OH-genkwanin and quercetin showed the stronger antigerminative activity at the concentration of 10 (4 M, whereas the radical elongation was reduced by rutin, isoquercetrin and 3?-OH-genkwanin. All compounds, tested at concentrations ranging between 10 (5 and 10 (7 M, showed stimulatory activities.

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“…Labdane-type diterpenoids occur abundantly in Leonurus sibiricus, 6) L. persicus, 7) and L. cardiaca.…”

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New Labdane-Type Diterpenoids from Leonurus heterophyllus SW.

Giang

Sơn²,

Matsunami

et al. 2005

Chem. Pharm. Bull.

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In Vietnamese traditional medicine, the plant Leonurus heterophyllus SW. is known as Ich mau thao, Sung uy, or Choi den. The dried aerial parts of L. heterophyllus (Herba Leonuri) are applicable in the treatment of menstrual pain and child birth, as well as high blood pressure, blood stasis, heart disorders, and dysentery. The dried ripe fruits (Fructus Leonuri) are used to treat edema and as a diuretic.1) Several prefuranic and furanic labdane-type diterpenoids were isolated in previous studies on L. heterophyllus collected in Guangdong province, China.2,3) It is well known that the chemical composition of plants is geographically varied, and the reason for that may be related to the ability of each species to cope with its habitat environment. Therefore we carried out systematic extraction and isolation of the L. heterophyllus species grown in Vietnam, which led to the structure determination of nine labdane-type diterpenoids, including five new compounds, designated leoheteronins A-E (5-9), two phytosterols as a mixture of b-sitosterol and stigmasterol, and the flavone genkwanin (10). The structures of the known diterpenoids hispanone (1), leoheterin (2), hispanolone (3), and galeopsin (4), and 10 were determined by comparing their physical ([a] D ) and spectroscopic data with the literature values.3-6) Compounds 2-4 were among the previous isolates from L. heterophyllus, 1 was isolated from Ballota species (Lamiaceae) 4) but for the first time from a Leonurus species, and 10 is considered to be a chemotaxonomic marker of the genus Leonurus.7) This paper deals with the structure elucidation of the five new labdane-type diterpenoids 5-9. Results and DiscussionThe extraction of the dried aerial parts of L. heterophyllus with MeOH and sequential fractionation using solvents of increasing polarity gave n-hexane-, ethyl acetate-, and 1-BuOHsoluble fractions. Separation of the n-hexane-soluble fraction with silica (Si) gel open-column chromatography, octadecyl Si (ODS) gel open-column chromatography, and repeated preparative ODS HPLC led to the isolation of compounds 1-10 together with a mixture of b-sitosterol and stigmasterol.Leoheteronin A (5) C-16)], six methylene and one methine groups, and two quaternary carbons. Analysis of the data suggested the structure of 5 to be 15,16-epoxylabda-8,13-diene-7,15-dione, which was confirmed on comparison of the NMR data with those of the related compound leopersin G. (Table 1) and 13 C-NMR (Table 2) (Table 1) and 13 C-NMR (Table 2) spectroscopic data showed that 7 was closely related to 5, and the presence of an additional hydroxyl group was deduced from the mass unit of 7. Five new natural labdane-type diterpenoids (5-9), designated leoheteronins A-E, together with four known diterpenoids (1-4), two phytosterols as a mixture of b b-sitosterol and stigmasterol, and the flavone genkwanin (10) were isolated from the aerial parts of Leonurus heterophyllus SW. (Lamiaceae) collected in northern Vietnam. Compound 1 was isolated for the first time from a Leonurus species, an...

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Labdane Diterpenes of Leonurus sibiricus

Cited by 58 publications

References 12 publications

New Bis-spirolabdane-Type Diterpenoids from Leonurus heterophyllus SW.

New Bis-spirolabdane-Type Diterpenoids from Leonurus heterophyllus SW.

In vitroallelopathic potential ofLeonurus sibiricusL. leaves

New Labdane-Type Diterpenoids from Leonurus heterophyllus SW.

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