Synthesis and absolute configuration of three natural ent-halimanolides with biological activity

Marcos, Isidro S.; Pedrero, A. B.; Sexmero, M. J.; Díez, David; Basabe, P.; Hernández, F.J. López; Urones, Julio G.

doi:10.1016/s0040-4039(02)02535-2

Cited by 28 publications

(16 citation statements)

References 33 publications

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“…This journal is © The Royal Society of Chemistry 2018 The study of genus Halimium plants has made possible to determine the presence of ve chemotypes of Halimiun viscosum, known in accordance with the harvesting place: Villarino de los Aires, (Salamanca, Spain), 17 La Fregeneda, (Salamanca, Spain), 26,27 Valparaiso, (Zamora, Spain), 28 Celorico da Beira, (Portugal) 29 and San João da Pesqueira, (Portugal). 30 In this group, the Euphorbiaceae, 78,108,109,[111][112][113][114] Cistaceae, 17,26,27,29,30,110,[115][116][117][118] Leguminoseae, 48,119,120 Compositae, 21,24 Jungermanniaceae, 121 Velloziaceae 52 and Annonaceae 122,123 plant families have been studied together with marine organisms of genus Spurilla 124 and Agelas. 74,125 The most numerous compounds of this group (Fig.…”

Section: Scheme 10mentioning

confidence: 99%

“…(1) ent-Halimanolides. 123,141,207,208 (2) Chettaphanin I and II. 109,209 (3) Bioactive sesterterpenolides.…”

Section: Ent-halimic Acid As Precursor Of Biologically Active Compounmentioning

confidence: 99%

“…109,209 (3) Bioactive sesterterpenolides. 123,[210][211][212] (4) Sesterterpenolides and glycerophospholipids hybrid compounds. 213 (5) Rearranged derivatives: ent-labdanes, 214 abeopicrasanes 215 and propellanes.…”

Section: Ent-halimic Acid As Precursor Of Biologically Active Compounmentioning

confidence: 99%

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Halimane diterpenoids: sources, structures, nomenclature and biological activities

et al. 2018

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Covering: 1970 to 2017 Diterpenes with a halimane skeleton constitute a small group of natural products that can be biogenetically considered as being between labdane and clerodane diterpenoids. Some of these compounds show biological activities, such as antitumour, mosquito repellency, germination inhibition and antimicrobial, as well as being biomarkers for tuberculosis. To the best of our knowledge, there are no reviews on these compounds. In this review, halimane skeleton diterpenoids are classified according to their biogenetic origin, characterization and/or the enzymes involved in their biosynthesis. Herein, a review of their synthesis or synthetic approaches is communicated.

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Section: Scheme 10mentioning

confidence: 99%

“…(1) ent-Halimanolides. 123,141,207,208 (2) Chettaphanin I and II. 109,209 (3) Bioactive sesterterpenolides.…”

Section: Ent-halimic Acid As Precursor Of Biologically Active Compounmentioning

confidence: 99%

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Halimane diterpenoids: sources, structures, nomenclature and biological activities

et al. 2018

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“…The residue was chromatographed on silica gel (hexane-EtOAc, 96:4) to obtain compound 6 (145.1 mg, 71%) as colorless oil. IR (neat) ν max / cm -1 : 2926, 2872, 1447, 1384, 1025, 873, 778, 599; 1 H NMR (CDCl 3 , 300 MHz) δ 0.71 (3H, s, 0.81 (3H, d, J 6.6 Hz,, 0.81 (3H, s, H-19), 1.00 -1.85 (15H, m), 2.00 -2.36 (2H, m), 2.79 (1H, dd, J 9.5; 11.0 Hz, 3.58 (1H, dd, J 2.4; 9.5 Hz, 6.24 (1H, brs, 7.19 (1H, brs, 7.34 (1H, brs,; 13 C NMR (CDCl 3 , 75.5 MHz) δ 11.2 (CH 2 , C-12), 13.9 (CH 3 , C-19), 16,8 (CH 3 -cleroda-15(16)-oxo-4(18),13(16),14-triene (7) AgF (101.2 mg, 0.8 mmol) was added to a solution of compound 6 (18.4 mg, 0.04 mmol) in dry pyridine (6.0 mL), and the reaction mixture was stirred for 23 h at room temperature under nitrogen. The crude product was filtered through a pad of Celite (5 cm) on silica gel using ethyl ether as eluent.…”

Section: Iodidementioning

confidence: 99%

“…14 Syntheses of some biologically active clerodanolides and ent-halimanolides were recently published 15,16 showing the importance of this new class of terpenoids. In connection with a previous study on the synthesis of some biological active hydroxybutenolide derivatives and regarding the use of the readily available methyl (+)-hardwickiate (1b) for the synthesis of natural products, 14,17,18 the clerodanes 2 and 3, enantiomers of two natural products, 4,10 have been synthesized (Figure 1).…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Ent-16-hydroxycleroda-4(18),13-dien-15,16-olide and Ent-cleroda-4(18),13-dien-15,16-olide from (+)-hardwickiic acid

Ide¹,

Costa²,

Imamura³

2006

J. Braz. Chem. Soc.

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As configurações absolutas de dois diterpenos butenolidos naturais foram confirmadas através da síntese do ent- 16-hidroxicleroda-4(18), 13-dien-15,16-olida (2) e ent-cleroda-4(18),13-dien-15,16-olida (3), enantiômeros de produtos naturais, a partir do ácido (+)-hardwickiico (1).The absolute configurations of two natural diterpene butenolides were confirmed through the synthesis of ent- 16-hydroxycleroda-4(18), 13-dien-15,16-olide (2) and ent-cleroda-4(18), 13-dien-15,16-olide (3), enantiomers of the natural products, starting from (+)-hardwickiic acid (1). Keywords: (+)-hardwickiic acid, clerodane, butenolide, absolute configuration IntroductionThe occurrence of natural clerodane diterpene butenolides and hydroxybutenolides has been reported in plants of the genera Polyalthia, 1-10 Acritopappus, 11 Premna, 12 and Cyathocalyx, 13 as well as their biological properties as antifeedants, 1 cytotoxicity to tumor cell cultures, 2,9 toxicity against Artemia salina 2,13 and Aedes aegypti, 13 febrifuges, 3 antimicrobials, 5,12 chewing sticks for sterilizing milk container, 12 and diuretics. 14 Syntheses of some biologically active clerodanolides and ent-halimanolides were recently published 15,16 showing the importance of this new class of terpenoids. In connection with a previous study on the synthesis of some biological active hydroxybutenolide derivatives and regarding the use of the readily available methyl (+)-hardwickiate (1b) for the synthesis of natural products, 14,17,18 the clerodanes 2 and 3, enantiomers of two natural products, 4,10 have been synthesized (Figure 1). Since only the relative stereochemistry was reported in the literature, the syntheses of 2 and 3 allowed to elucidate the absolute stereochemistry of the compounds isolated from Polyalthia longifolia Thw. 4 Results and DiscussionThe reduction of carbomethoxy group of 1b to the corresponding methyl group and isomerization of endocyclic double bond to exocyclic double bond in order to obtain a desired A ring functionality of the structures 2 and 3, a dehydration reaction of the known alcohol 4 18 was considered. Although the alcohol 4 was prepared previously in a reasonable yield through the reduction of (+)-methyl hardwickiate (1b) using an excess of sodium in propan-1-ol, a mixture with corresponding carboxylic acid was always obtained. 18 Thus, the crude product was first treated with diazomethane and then submitted to the reduction with lithium aluminum hydride to furnish the desired alcohol 4 in 59% overall yield. (Scheme 1)In a previous study 19 it was observed that the elimination reaction of the corresponding sulfonic ester (-OTs or -OMs) using basic conditions (DBU, t BuO -K + ) led to the desired olefin in a low yield and recovering the starting material. To detour this problem the dehydroiodination reaction was considered. Mesylation of alcohol 4 with methanesulfonyl chloride followed by treatment with sodium iodide gave the corresponding iodide 6 in 50% yield. Next, the dehydroiodination reaction of 6 was performed using silver fluori...

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Diterpene Acids as Starting Materials for the Synthesis of Biologically Active Compounds

Tobal¹,

Roncero²,

Moro³

et al. 2022

Chiral Building Blocks in Asymmetric Synthesis

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Synthesis and absolute configuration of three natural ent-halimanolides with biological activity

Cited by 28 publications

References 33 publications

Halimane diterpenoids: sources, structures, nomenclature and biological activities

Halimane diterpenoids: sources, structures, nomenclature and biological activities

Synthesis of Ent-16-hydroxycleroda-4(18),13-dien-15,16-olide and Ent-cleroda-4(18),13-dien-15,16-olide from (+)-hardwickiic acid

Diterpene Acids as Starting Materials for the Synthesis of Biologically Active Compounds

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