- Thunberginols A, B, and F, new antiallergic and antimicrobial principles from hydrangeae dulcis folium.
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Six new antiallergic and antimicrobial principles, thunberginols A, B, C, D, E, and F, were isolated from Hydrangeae Dulcis Folium, the fermented and dried leaves of Hydrangea macrophylla SERINGE var. thunbergii MAKINO. The chemical structures of thunberginols A, B, and F have been determined on the basis of chemical and physiocochemical evidence. Thunberginols A, B, and F showed more potent antiallergic activity than phyllodulcin, hydrangenol, and AA-861 in the in vitro test using the Schults-Dale reaction in sensitized guinea pig bronchial muscle. Thunberginols A, B, and F also exhibited antimicrobial activity against oral bacteria.
- Yoshikawa,Uchida,Chatani,Murakami,Yamahara
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- Differentiation inducing activities of isocoumarins from Hydrangea Dulcis Folium.
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In the course of searching for differentiation inducers against leukemic cells from plants, we have recognized the differentiation inducing activities of the methanolic extract of Hydrangea Dulcis Folium. Activity guided separation of the extract was carried out using M1 cells, and seven isocoumarins were isolated as active substances. These isocoumarins showed the activities at the concentration of 100 microM and non-cytotoxic effects even at 300 microM.
- Umehara,Matsumoto,Nakamura,Miyase,Kuroyanagi,Noguchi
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- Reaction of arynes with trifluoroacetylated β-diketones: Novel formation of isocoumarins and phenanthrenes
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Polysubstituted isocoumarins were synthesized by the reaction of substituted 2-(trimethylsilyl)aryl triflates with trifluoromethylated β-diketones in the presence of CsF. The reaction proceeded through carbon-carbon bond insertion of aryne and intramolecular cyclization to form intermediates of alcohol anions, which extruded trifluoromethyl anion to afford isocoumarins. By using CuBr as a catalyst, 2 eq. of aryne reacted with β-diketones to afford phenanthrenes and 1,2-diarylethanones. Although reaction of 2-(trimethylsilyl)phenyl triflate with 1,1,1-trifluoro-4′-methylbenzoylacetone in the presence of CsF gave 3-(4′-methylphenyl)isocoumarin in 67% yield, addition of 0.2 eq. of CuCN resulted in the formation of 9-(4-methylbenzoyl)-10-trifluoromethylphenanthrene in 35% yield.
- Okuma, Kentaro,Tanabe, Yukiko,Fukami, Takuto,Ishibashi, Yuto
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- Novel one-pot synthesis of polysubstituted isocoumarins from arynes and trifluoroacetylated β-diketones
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Polysubstituted isocoumarins such as thunberginol A were synthesized by the reaction of substituted 2-(trimethylsilyl)-phenyl triflate with trifluoromethylated β-diketones in the presence of CsF. The reaction proceeded via carboncarbon bond insertion of aryne followed by intramolecular cyclization and CF3 anion extrusion. The C(..O)CF3 unit has high potential for not only the nucleophilic moiety but also a useful leaving group of CF3.
- Okuma, Kentaro,Hirano, Koki,Tanabe, Yukiko,Itoyama, Ryoichi,Miura, Atsumi,Nagahora, Noriyoshi,Shioji, Kosei
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supporting information
p. 492 - 494
(2014/04/17)
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- Palladium-catalyzed aryl halide carbonylation-intramolecular O-enolate acylation: Efficient isocoumarin synthesis, including the synthesis of thunberginol A
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Exposure of a series of a-(o-haloaryl)-substituted ketones to palladium-catalyzed carbonylation conditions leads to the formation of the corresponding isocoumarins. Balloon pressure of CO is sufficient to achieve high yielding reactions, and both cyclic a
- Tadd, Andrew C.,Fielding, Mark R.,Willis, Michael C.
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supporting information; experimental part
p. 6744 - 6746
(2010/03/25)
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- Synthesis of 3-substituted isocoumarins and their inhibitory effects on degranulation of RBL-2H3 cells induced by antigen
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Eleven 3-substituted isocoumarins and a benzylidenephthalide were synthesized through thermal cyclization reaction of δ- and γ-ketoamides, respectively. Subsequent deprotection of the hydroxyl groups of the resulting isocoumarin and benzylidenephthalide compounds afforded thunberginols A, B, and F., respectively, which originated from the processed leaves of Hydrangea macrophylla Seringe var. thunbergii MAKINO. The synthesized isocoumarins and thunberginols were evaluated for their anti-allergic activity, in which thunberginol B exhibited the highest inhibitory potency on the degranulation of RBL-2H3 cells induced by antigen. Structure - activity relationship studies were carried out to determine the necessary substituents on the 3-phenylisocoumarin skeleton for inhibitory activity.
- Kurume, Ai,Kamata, Yasuhiro,Yamashita, Masayuki,Wang, Qilong,Matsuda, Hisashi,Yoshikawa, Masayuki,Kawasaki, Ikuo,Ohta, Shunsaku
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experimental part
p. 1264 - 1269
(2009/09/25)
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- Synthesis of 3-arylisocoumarins, including thunberginols A and B, unsymmetrical 3,4-disubstituted isocoumarins, and 3-ylidenephthalides via iodolactonization of methyl 2-ynylbenzoates or the corresponding carboxylic acids
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3-Aryl-4-iodoisocoumarins, which were readily and efficiently prepared by regioselective iodolactonization of methyl 2-ynylbenzoates or the corresponding carboxylic acids, were used as precursors either to 3-arylisocoumarins, including naturally-occurring
- Rossi, Renzo,Carpita, Adriano,Bellina, Fabio,Stabile, Paolo,Mannina, Luisa
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p. 2067 - 2081
(2007/10/03)
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- New procedures for the selective synthesis of 2(2H)-pyranone derivatives and 3-aryl-4-iodoisocoumarins
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5-Iodo-2(2H)-pyranone derivatives have been selectively synthesized by reaction of stereodefined methyl 2-en-4-ynoates with iodine in MeCN, CH2Cl2 or C6H6 at 20°C (Method C) or by treatment of these esters with
- Biagetti, Matteo,Bellina, Fabio,Carpita, Adriano,Stabile, Paolo,Rossi, Renzo
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p. 5023 - 5038
(2007/10/03)
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- Development of bioactive functions in Hydrangeae Dulcis Folium. VI. Syntheses of thunberginols A and F and their 3'-deoxy-derivatives using regiospecific lactonization of stilbene carboxylic acid: Structures and inhibitory activity on histamine release of hydramacrophyllols A and B
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Lactonization reaction of 2-carboxystilbene mediated by copper(II) chloride proceeded regiospecifically to give the five-membered lactone, while the bromolactonizations using N-bromosuccinimide and anodic oxidation were found to furnish the six-membered lactone. Using these regiospecific lactonization reactions as a key step, antiallergic and antimicrobial isocoumarins and the benzylidenephthalides thunberginols A and F and their 3'-deoxyanalogs were synthesized from phyllodulcin and hydrangenol. Two phthalides called hydramacrophyllols A and B were isolated from Hydrangeae Dulcis Folium and their stereostructures were determined on the basis of physicochemical and chemical evidence, which included the syntheses of hydramacrophyllols A and B from hydrangenol by the application of the lactonization method using copper(II) chloride. In addition, hydramacrophyllols A and B were found to exhibit an inhibitory effect on the histamine release from rat peritoneal exudate cells induced by antigen- antibody reaction.
- Yoshikawa, Masayuki,Shimada, Hiromi,Yagi, Nobuhiro,Murakami, Nobutoshi,Shimoda, Hiroshi,Yamahara, Johji,Matsuda, Hisashi
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p. 1890 - 1898
(2007/10/03)
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- Chemical transformation from dihydroisocoumarin into benzylidene-phthalide by use of regiospecific oxidative lactonization mediated by copper chloride (H) - Syntheses of thunberginol F and hydramacrophyllol A and B
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Oxidative lactonization of 2-carboxystilbene mediated by CuCl2 proceeded regiospecifically to give the five-membered lactone. By utilizing this lactonization as a key reaction, chemical transformation from dihydroisocoumarine into benzylideneph
- Yoshikawa,Harada,Yagi,Okuno,Muraoka,Koyama,Murakami
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p. 721 - 723
(2007/10/02)
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- Synthesis of 3-substituted isocoumarins and related natural products
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Several N,N-diethyl-2-acylmethylbenzamides (6) were prepared from N,N- diethyl-2-toluamides (4), and the ketoamides (6) were easily cyclized to the corresponding 3-substituted isocoumarins (8) by heating in acetic acid or xylene. This simple procedure was
- Ohta,Kamata,Inagaki,Masuda,Yamamoto,Yamashita,Kawasaki
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p. 1188 - 1190
(2007/10/02)
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