Clerodane and ent-halimane diterpenes from polyalthia longifolia

Hara, Noriyuki; Asaki, Hitomi; Fujimoto, Yoshinori; Gupta, Yogesh; Singh, Ashish Kumar; Sahai, Mahendra

doi:10.1016/0031-9422(94)00583-f

Cited by 81 publications

(82 citation statements)

References 19 publications

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“…In this manner the desired lactone 3 was obtained in 71% yield from 2. Lactone 3 was characterized through physical and spectroscopic analyses and showed good agreement with data reported for the enantiomer, 4 …”

Section: Resultssupporting

confidence: 65%

“…The 1 H NMR spectra of 2 showed signals at δ 5.98 (H-16) and at δ 5.81 (H-14) which were in good agreement with those observed in the literature (δ 6.00 and 5.80, respectively) for the enantiomer. 4 Other spectroscopic and physical data of 2 were also in agreement with those reported for the enantiomer, except the sign of optical rotation, which was -14) and at δ 6.00 (H-15) confirmed the α-substituted hydroxybutenolide moiety and are in agreement with those observed in the literature for the model compound. 21 For the synthesis of lactone 3, hydroxybutenolide 2 (or a mixture containing 2 and 8) was treated with sodium borohydride in methanol according to a described procedure.…”

supporting

confidence: 88%

“…The occurrence of natural clerodane diterpene butenolides and hydroxybutenolides has been reported in plants of the genera Polyalthia, [1][2][3][4][5][6][7][8][9][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.…”

Section: Introductionmentioning

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). 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.…”

Section: Introductionmentioning

confidence: 99%

“…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 …”

Section: Introductionmentioning

confidence: 99%

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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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Section: Resultssupporting

confidence: 65%

supporting

confidence: 88%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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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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Structurally Diverse Diterpenoids from the Sanya Bay Nudibranch Hexabranchus sanguineus and Its Sponge‐Prey Chelonaplysilla sp.

Shen

Su³

et al. 2023

Chemistry A European J

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Investigation of the South China Sea nudibranch Hexabranchus sanguineus from Sanya Bay afforded, in addition to three known compounds, nine new diterpenoids of the 5,19‐cycloclerodane‐ (sanyanolides A–D), clerodane‐ (sanyanolide E) and subersin‐ (sanyanolides F–I) type. Remarkably, six diterpenoids aforementioned from H. sanguineus were also isolated from the sponge Chelonaplysilla sp. from the same water region, suggesting a trophic relationship between H. sanguineus and Chelonaplysilla sp. The structure and absolute configuration of new compounds were established by a combination of spectroscopic data, X‐ray diffraction analysis and/or time‐dependent density functional theory/electronic circular dichroism calculations. A plausible biogenetic relationship between these diterpenoids, along with the chemo‐ecological implications of their co‐occurrence in the two organisms investigated, was proposed and discussed. In in vitro bioassays, echinoclerodane A exhibited a potent inhibitory effect (IC50=2.81 μM) on LPS‐induced inflammatory response in RAW 264.7 macrophage cells. In addition, echinoclerodane A and oculatolide showed considerable antibacterial activities with MIC values ranging from 1.0 to 8.0 μg/mL.

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The key role of ¹³C NMR analysis in the identification of individual components of Polyalthia longifolia leaf oil

Ouattara

Boti

Ahibo

et al. 2014

Flavour & Fragrance J

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Polyalthia longifolia produces sesquiterpene-rich essential oils (EOs) whose compositions varied substantially from sample to sample depending on the origin of the plant (Nigeria and Vietnam). Nothing is known about the phytochemistry of Ivoirian P. longifolia. The aim of the present study was to characterize Ivoirian P. longifolia through the chemical composition of the leaf oil and to develop a strategy that allows the identification of minor oxygenated sesquiterpenes whose MS data are not compiled in commercial or laboratory-constructed MS libraries. The EO was submitted to gas chromatography (GC) retention index (RI), GC-mass spectrometry (MS) and 13 C nuclear magnetic resonance (NMR) analysis. Then hydrocarbons and oxygenated components were separated and the oxygenated fraction was chromatographed on silica gel. The fractions were analysed by GC(RI) and 13 C NMR. Seventy compounds accounting for 91.8% of the EO were identified. Sesquiterpene hydrocarbons, (E)-β-caryophyllene (27.8%), α-zingiberene (20.0%) and allo-aromadendrene (15.0%), were the major components. Various oxygenated sesquiterpenes whose MS data were not compiled in commercial and laboratory-made MS libraries were identified by comparison of their chemical shift values in the spectrum of the fraction of CC with those reported in the literature and compiled in a laboratory-constructed 13 C NMR data library. The composition of the investigated Ivoirian P. longifolia oil sample presented similarities and differences with Nigerian and Vietnamese oils. Combined analysis of Ivoirian P. longifolia EO by chromatographic and spectroscopic techniques including 13 C NMR without isolation of the components, appeared particularly efficient to identify minor components of EOs, whose MS spectra are insufficiently differentiated or MS data are not compiled in commercial and lab-constructed MS libraries.

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Clerodane and ent-halimane diterpenes from polyalthia longifolia

Cited by 81 publications

References 19 publications

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

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

Structurally Diverse Diterpenoids from the Sanya Bay Nudibranch Hexabranchus sanguineus and Its Sponge‐Prey Chelonaplysilla sp.

The key role of ¹³C NMR analysis in the identification of individual components of Polyalthia longifolia leaf oil

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Clerodane and ent-halimane diterpenes from polyalthia longifolia

Cited by 81 publications

References 19 publications

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

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

Structurally Diverse Diterpenoids from the Sanya Bay Nudibranch Hexabranchus sanguineus and Its Sponge‐Prey Chelonaplysilla sp.

The key role of 13C NMR analysis in the identification of individual components of Polyalthia longifolia leaf oil

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The key role of ¹³C NMR analysis in the identification of individual components of Polyalthia longifolia leaf oil