The Transformation of Glaucolide A into Cadinanolides and Hirsutinolides

Martínez‐Vázquez, Mariano; Sepúlveda, Santiago A.; Belmont, Marco A.; Rubio, M.; Joseph‐Nathan, Pedro

doi:10.1021/np50085a007

Cited by 12 publications

(6 citation statements)

References 19 publications

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“…The choice of this silica-gel-free purification technique aimed to avoid any degradation that could change the SL profile of L. chamissonis . As mentioned before, the silica gel stationary phase increases the possibility of structure modification of SLs during the chromatographic purification [ 14 ]. Glaucolide B ( 1 ) was subjected to various chemical modifications using different Lewis and Brønsted–Lowry acids (BiCl 3 , SOCl 2 , Ac 2 O, and TFA; pKa −0.25) and bases (DMAP, pKa 9.5; K 2 CO 3 , pKa 10.3) to explore its chemical behavior.…”

Section: Resultsmentioning

confidence: 99%

“…Some previous studies carried out reactions mimicking the chromatographic purification of SLs, demonstrating that silica gel caused the conversion of glaucolide into hirsutinolide [ 11 ] and cadinanolide [ 12 , 13 ]. A similar goal was reached when various hirsutinolides and cadinanolides were obtained after treating glaucolide A in methanol (MeOH) or ethanol (EtOH) with alumina or silica gel [ 14 ]. Likewise, the acidic absorbent bentonite (composed of metallic oxides) was used to prepare 5β-hydroxy-hirsutinolide from glaucolide B [ 15 ].…”

Section: Introductionmentioning

confidence: 95%

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Semisynthetic Sesquiterpene Lactones Generated by the Sensibility of Glaucolide B to Lewis and Brønsted–Lowry Acids and Bases: Cytotoxicity and Anti-Inflammatory Activities

et al. 2023

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Sesquiterpene lactone (SL) subtypes including hirsutinolide and cadinanolide have a controversial genesis. Metabolites of these classes are either described as natural products or as artifacts produced via the influence of solvents, chromatographic mobile phases, and adsorbents used in phytochemical studies. Based on this divergence, and to better understand the sensibility of these metabolites, different pH conditions were used to prepare semisynthetic SLs and evaluate the anti-inflammatory and antiproliferative activities. Therefore, glaucolide B (1) was treated with various Brønsted–Lowry and Lewis acids and bases—the same approach was applied to some of its derivatives—allowing us to obtain 14 semisynthetic SL derivatives, 10 of which are hereby reported for the first time. Hirsutinolide derivatives 7a (CC50 = 5.0 µM; SI = 2.5) and 7b (CC50 = 11.2 µM; SI = 2.5) and the germacranolide derivative 8a (CC50 = 3.1 µM; SI = 3.0) revealed significant cytotoxic activity and selectivity against human melanoma SK-MEL-28 cells when compared with that against non-tumoral HUVEC cells. Additionally, compounds 7a and 7c.1 showed strongly reduced interleukin-6 (IL-6) and nitrite (NOx) release in pre-treated M1 macrophages J774A.1 when stimulated with lipopolysaccharide. Despite the fact that hirsutinolide and cadinanolide SLs may be produced via plant metabolism, this study shows that acidic and alkaline extraction and solid-phase purification processes can promote their formation.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 95%

Semisynthetic Sesquiterpene Lactones Generated by the Sensibility of Glaucolide B to Lewis and Brønsted–Lowry Acids and Bases: Cytotoxicity and Anti-Inflammatory Activities

et al. 2023

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“…A soln. of 5 (160 mg) in CHCl 3 (40 ml) was shaken in the presence of silica gel (SiO 2 ; 4.8 g) during 48 h at r.t. [19]. When no glaucolide A (5) was detected by TLC in the reaction mixture, the soln.…”

Section: Experimental Partmentioning

confidence: 98%

Molluscicidal Sesquiterpene Lactones from Species of the Tribe Vernonieae (Compositae)

Borkosky

León

Juárez

et al. 2009

Chemistry & Biodiversity

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Schistosomiasis is caused by parasitic flatworms of the genus Schistosoma, and some snails, particularly of the genus Biomphalaria (Planorbidae), are directly implicated in the transmission of the disease. Continuing with our investigations of bioactive plant constituents, we evaluated and report in the present article, the molluscicidal effects of 16 sesquiterpene lactones, as well as the commercial reagents tetrahydrofuran, furfural, and furfuryl alcohol, on an adult population of B. peregrina. The natural sesquiterpene lactones tested are characteristic constituents of species of the tribe Vernonieae, family Asteraceae. Compounds 1-3 and 7 came from a Bolivian collection of Vernonanthura pinguis, compounds 4 and 5 from an Argentine collection of Cyrtocymura cincta var. cincta, 6 was obtained from a Bolivian collection of Eirmocephala megaphylla, 8-14 from an Argentine collection of Centratherum punctatum ssp. punctatum, and compounds 15 and 16 were obtained by chemical derivatization from 5 and 14, respectively. Ten of the sesquiterpene lactones displayed moderate molluscicidal activity (LD50<100 microg/ml). Commercial reagents were inactive.

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“…For studying correlation "structure-activity", modifications of artemisinin lactone cycle (18) and artemisinin derivative (21) were carried out. Watersoluble acids (24 а-m) were among the obtained compounds (22-24) [25].…”

Section: Artemisinin Isolating Technology and Ways To Obtain Its Deri...mentioning

confidence: 99%

Natural Sesquiterpene Lactones as Renewable Chemical Materials for New Medicinal Products

Адекенов¹

2013

Eur Chem Tech J

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Literature data and own research results on the technology for isolating natural sesquiterpene lactones such as arglabin, alantolactone, artemisinin, grosheimin, isoalantolactone, parthenolide, santonin and potential possibilities of their use as renewable material for obtaining new compounds as well as biologically active derivatives are generalized in this review. Sesquiterpene lactones from plants are promising sources for the development and practical application of new original medical products possessing antitumor, anti-inflammatory, antimalarial, antiulcer, antiviral and immune-stimulating action. The technology for isolating sesquiterpene lactones is based on the extraction of raw plant material by different organic solvents with the subsequent chromatographic purification. The effective and environmentally safe technology for isolation and purification of sesquiterpene lactone arglabin from Artemisia glabella Kar. et Kir. by the СО2-extraction method is developed. Thereat, it was experimentally determined that the method for isolating arglabin from CO2 extract of Artemisia glabella Kar. et Kir. using centrifugal partition chromatography is effective for preparative isolation of the active substance and its manufacturing application. It is practically important to obtain water-soluble derivatives of biologically active sesquiterpene lactones and also to use the nanotechnology achievements for directed transportation of a molecule of the medicine in the human body thereby reducing toxicity of an active component. Promising direction is chemical modification of molecules in sesquiterpene lactones which are renewable material for obtaining new derivatives, thanks to which it becomes possible to solve two problems at the same time. Firstly, these researches help to obtain derivatives with higher biological activity or improved physical and chemical properties. Secondly, these researches enable us to disclose the mechanism of action of different medicines within the framework of “structure-activity” correlation. The article presents the literature data and own results on chemical modification of sesquiterpene lactones of alantolactone, arglabin, artemisinin, grosheimin, isoalantolactone, parthenolide and santonin. Various reactions on functional groups of these molecules were used to obtain a number of new derivatives of sesquiterpene lactones containing haloid-, pyrazole-, triazole-, amino-, dialkylamino-, hydroxy-, dialkyl phosphonate- and cyclopropane groups, which have shown high physiological activity.

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The Transformation of Glaucolide A into Cadinanolides and Hirsutinolides

Cited by 12 publications

References 19 publications

Semisynthetic Sesquiterpene Lactones Generated by the Sensibility of Glaucolide B to Lewis and Brønsted–Lowry Acids and Bases: Cytotoxicity and Anti-Inflammatory Activities

Semisynthetic Sesquiterpene Lactones Generated by the Sensibility of Glaucolide B to Lewis and Brønsted–Lowry Acids and Bases: Cytotoxicity and Anti-Inflammatory Activities

Molluscicidal Sesquiterpene Lactones from Species of the Tribe Vernonieae (Compositae)

Natural Sesquiterpene Lactones as Renewable Chemical Materials for New Medicinal Products

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