Diterpenes from Arnica angustifolia

Schmidt, Thomas J.; Paßreiter, Claus M.; Wendisch, Detlef; Willuhn, Günter

doi:10.1016/0031-9422(95)00304-p

Cited by 16 publications

(38 citation statements)

References 19 publications

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“…()-Sclareolide (10), a constituent of Arnica angustifolia [20], Sideritis nutans [21], and Kyllinga erecta [22], has exhibited phytotoxic activity and cytotoxicity against human cancer cell lines [6] [23]. Compound 10 differs from 1 only in the presence of an oxo group at C (12).…”

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confidence: 99%

Microbial Transformation of Sesquiterpenes, (−)‐Ambrox^® and (+)‐Sclareolide

Choudhary

Musharraf

Sami

et al. 2004

Helvetica Chimica Acta

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The microbial transformation of (À)-Ambrox ¾ (1), a perfumery sesquiterpene, by a number of fungi, by means of standard two-stage-fermentation technique, afforded ambrox-1a-ol (2), ambrox-1a,11a-diol (3), ambrox-1a,6a-diol (4), ambrox-1a,6a,11a-triol (5), ambrox-3-one (6), ambrox-3b-ol (7), ambrox-3b,6b-diol (8), 13,14,15,16-tetranorlabdane-3,8,12-triol (9), and sclareolide (10) (Schemes 1 and 2). Further incubation of compound 10 with Cunninghamella elegans afforded 3-oxosclareolide (11), 3b-hydroxysclareolide (12), 2a-hydroxysclareolide (13), 2a,3b-dihydroxysclareolide (14), 1a,3b-dihydroxysclareolide (15), and 3b-hydroxy-8-episclareolide (16) (Scheme 3). Metabolites 2 ± 5, 12, 13, and 16 were found to be new compounds. The major transformations include a reaction path involving hydroxylation, ether-bond cleavage and inversion of configuration. Metabolites 11 ± 16 of sclareolide showed significant phytotoxicity ( Table 1). The structures of the metabolites were characterized on the basis of spectroscopic techniques.Introduction. ± In continuation of our studies on biotransformation of bioactive natural and synthetic compounds [1 ± 11], we have recently investigated the biotransformation of two sesquiterpenes, (À)-Ambrox ¾ (1) and ()-sclareolide (10), with various fungal strains. Ambergris, a metabolite of the sperm whale, is one of the mostvaluable animal perfumes, ranking with civet and musk [12] [13]. Ambrein is the major constituent of the ambergris. During exposure in the sea for many years, ambrein is oxidatively decomposed by the action of sea water, air, and sunlight to yield some other odorous compounds [14]. In these compounds, (À)-Ambrox ¾ (1) has a very strong amber-like odor.Fermentation of (À)-Ambrox ¾ (1) with Fusarium lini (NRRL 68751) afforded the new mono-, di-, and trihydroxylated metabolites 2 ± 5, as a result of enantioselective ahydroxylations at C(1), C(6), and C(11), while incubation of compound 1 with Rhizopus stolonifer (ATCC 10404) yielded metabolites 6 ± 8 and ether-cleaved product 9. The ether cleavage through biotransformation is a rare observation. Fermentation of compound 1 with Curvularia lunata (NRRL 2178) yielded metabolites 6 and 7, while its biotransformation with Cunninghamella elegans (NRRL 1392) afforded compounds 6, 7, and ()-sclareolide (10). Compounds 6 ± 10 have already been reported as metabolites of 1 by Cephalosporium aphidicola (wild type), Aspergillus niger (IFO 4049), Aspergillus cellulose (IFO 4040), and Botryatis cinerea (AHU 9424) [15 ± 19]. The oxygenated metabolites of compound 1 did not release any effective odor when compared to 1, except for the ether-cleaved product 9, which exhibited a strong sweet odor quit different from the amber-like odor.

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confidence: 99%

Microbial Transformation of Sesquiterpenes, (−)‐Ambrox^® and (+)‐Sclareolide

Choudhary

Musharraf

Sami

et al. 2004

Helvetica Chimica Acta

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“…Thus, 1 was suggested to be a 9‐hydroxylabd‐13‐ene diterpenoids (Giang et al ., 2005a). The configuration of the double bond at the side chain was determined to be E by observing the signal for both allylic protons at δ 4.27 (2H, dd, 6.8, 2.0 Hz, H‐15) since the Z ‐isomer would have shown two distinct dd signals (Schmidt et al ., 1995; Giang et al ., 2005a). The relative stereochemistry of 1 was determined by nuclear Overhauser enhancement and exchange spectroscopy (NOESY) (Fig.…”

Section: Resultsmentioning

confidence: 99%

Labdane‐type diterpenoids from Leonurus heterophyllus and their cholinesterase inhibitory activity

Hung

Luan

Cuong

et al. 2010

Phytotherapy Research

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In the course of screening plants used in natural medicines as memory enhancers, a 70% ethanol extract of the aerial parts of Leonurus heterophyllus showed significant AChE inhibitory activity. Bioassay-guided fractionation and repeated column chromatography led to the isolation of a new labdane-type diterpenoids (1), named leoheteronin F, and six known compounds (2-7). The chemical structures of isolated compounds were elucidated based on extensive 1D and 2D NMR spectroscopic data. The isolates 1-7 were investigated in vitro for their anticholinesterase activity using mouse cortex AChE enzyme. Leoheteronin A (5) and leopersin G (7), which possess a 15,16-epoxy group at the side chain, were found to be potent in the inhibition of AChE.

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“…3 and the EtOAc extract. They were 18 diterpenoids: abieta-7,13-diene-18-oic acid (4, 680 mg), 19) 18-succinyloxyabieta-8,11,13-triene methyl ester (6, 110 mg), 20) 15,18-dihydroxyabieta-8,11,13-trien-7-one (7, 53 mg), 21) 15-hydroxy-7-oxo-8,11,13-abietatrien-18-oic acid (8, 26 mg), 22) abiesadine R (9, 102.4 mg), 9 15-hydroxydehydroabietic acid (10, 68.9 mg), 12) abiesadine I (11, 157 mg), 9) 9,13b-epidioxy-8(14)-abieten-18-oic acid (12, 62.5 mg), 11) abiesadine X (14, 286 mg), 9) manool (15, 34.6 mg), 23) torreferol (16, 18.6 mg), 24) abiesadine Y (17, 40.7 mg), labd-13(Z)-ene-8a,15-diol (18, 88.6 mg), 25) manoyl oxide (19, 3.8 mg), 26) 8-epimanoyl oxide (20, 3.8 mg), 27) phytol (21, 209.5 mg), 28) abiesanordine F (23, 124 mg), 4) 2-hydroxynaringenin (35, 990 mg), 38) pallasiin (36, 908 mg), 39) apigenin (37, 8.9 mg), 40) myricetin (39, 12.2 mg), 41) 4Ј,5-dihydroxy-3,7-dimethoxy-6-methylflavone (40, 70 mg) 42) ; 12 lignans: (7ЈS,8ЈR)-dihydrodehydrodiconiferyl alcohol (41, 22.8 mg), 43) 67) Briefly, compound 3 (10 mg) was dissolved in 5 ml HCl (10%), and kept refluxing at 75°C. After 2 h, the reaction was stopped and the mixture was extracted by EtOAc.…”

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confidence: 99%

Systematic Phytochemical Investigation of Abies spectabilis

et al. 2010

Chem. Pharm. Bull.

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Abies is an important genus of the Pinaceae family comprising about 50 species around the world. Plants of this genus show high diversity in their secondary metabolites as well as pharmacological effects.1) Previously, we reported the occurrence of a unique sesquiterpenoid, a novel biflavanol, some diterpenoids, norditerpnoids, triterpnoids, and other compounds from three different Abies plants of A. georgei, A. delabayi, and A. chensiensis. 2-9) Abies spectabilis (D. DON) spach is a tall evergreen tree distributed mainly in East Asia-Himalayas from Afghanistan to Nepal. 10) To date, no phytochemical study has been reported on this species. As a continuation of the research analyzing the chemical constituents form Abies species in China, A. spectabilis was selected and subjected to a systematic phytochemical investigation, which led to the isolation of 3 new ( Fig. 1) and 69 known chemical components. In this paper, we report the isolation and structure elucidation of the new compounds. Meanwhile, the cytotoxic activities of all three new compounds against four tumor cell lines are also described. Results and DiscussionThe CHCl 3 extract of whole plants of Abies spectabilis was subjected to silica gel, RP-18, and Sephadex LH-20 column chromatographic purification, as well as repeated preparative (prep.) TLC to yield two new diterpenes and 35 known compounds. By similar procedures, one new flavone and 34 known compounds were separated from the EtOAc extract.Compound 1 C-13)]. In the double quantunum fluorescein (DQF) correlation spectroscopy (COSY) experiment, the correlations of H-1 through H-2 to H-3; H-5 to H-6, H-9 through H-11 to H-12, and H-15 to H-16,17 established four fragments. The planar structure can be deduced as shown in Fig. 1 according to the heteronuclear multiple bond connectivity (HMBC) correlations traced from four methyls 17,19,20), methoxyl, and olefinic protons. Based on the small coupling constant of H-12 ( 3 J H11,H12 ϭ 2.9 Hz), the configuration of C12-OMe was deduced as axial-orientation.11) This could also be confirmed by the nuclear Overhauser effect spectroscopy (NOESY) correlations of H 3 -20 to H 3 -19/H-11 and H-9 to H-5/12-OMe. Therefore, compound 1 was concluded to be abieta-7,13-diene-12a-methoxy-18-oic acid.Compound 2 was found to possess the molecular formula

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Diterpenes from Arnica angustifolia

Cited by 16 publications

References 19 publications

Microbial Transformation of Sesquiterpenes, (−)‐Ambrox^® and (+)‐Sclareolide

Microbial Transformation of Sesquiterpenes, (−)‐Ambrox^® and (+)‐Sclareolide

Labdane‐type diterpenoids from Leonurus heterophyllus and their cholinesterase inhibitory activity

Systematic Phytochemical Investigation of Abies spectabilis

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Diterpenes from Arnica angustifolia

Cited by 16 publications

References 19 publications

Microbial Transformation of Sesquiterpenes, (−)‐Ambrox® and (+)‐Sclareolide

Microbial Transformation of Sesquiterpenes, (−)‐Ambrox® and (+)‐Sclareolide

Labdane‐type diterpenoids from Leonurus heterophyllus and their cholinesterase inhibitory activity

Systematic Phytochemical Investigation of Abies spectabilis

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Microbial Transformation of Sesquiterpenes, (−)‐Ambrox^® and (+)‐Sclareolide

Microbial Transformation of Sesquiterpenes, (−)‐Ambrox^® and (+)‐Sclareolide