Synthesis of icariin from kaempferol through regioselective methylation and <i>para</i>-Claisen–Cope rearrangement

Mei, Qinggang; Wang, Chun; Zhao, Zhigang; Yuan, Wei‐Cheng; Zhang, Guolin

doi:10.3762/bjoc.11.135

Cited by 24 publications

(23 citation statements)

References 31 publications

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“…For glycosylation of flavone 4 , 2,3,4,6-tetra- O -acetyl-α- d -glucopyranosyl bromide ( 8 ) was selected as glucose donor and two reaction methods were applied: a Koenigs-Knorr method [ 33 , 34 , 35 ] and a modified Michael method [ 36 ]. Both reactions were carried out at room temperature to decrease the number of side products [ 37 ].…”

Section: Resultsmentioning

confidence: 99%

Synthesis of New Glycosylated Flavonoids with Inhibitory Activity on Cell Growth

et al. 2018

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Natural flavonoids and xanthone glycosides display several biological activities, with the glycoside moiety playing an important role in the mechanism of action of these metabolites. Herein, to give further insights into the inhibitory activity on cell growth of these classes of compounds, the synthesis of four flavonoids (5, 6, 9, and 10) and one xanthone (7) containing one or more acetoglycoside moieties was carried out. Acetyl groups were introduced using acetic anhydride and microwave irradiation. The introduction of one or two acetoglycoside moieties in the framework of 3,7-dihydroxyflavone (4) was performed using two synthetic methods: the Michael reaction and the Koenigs-Knorr reaction. The in vitro cell growth inhibitory activity of compounds 5, 6, 7, 9, and 10 was investigated in six human tumor cell lines: A375-C5 (malignant melanoma IL-1 insensitive), MCF-7 (breast adenocarcinoma), NCI-H460 (non-small cell lung cancer), U251 (glioblastoma astrocytoma), U373 (glioblastoma astrocytoma), and U87MG (glioblastoma astrocytoma). The new flavonoid 3-hydroxy-7-(2,3,4,6-tetra-O-acetyl-β-glucopyranosyl) flavone (10) was the most potent compound in all tumor cell lines tested, with GI50 values < 8 μM and a notable degree of selectivity for cancer cells.

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Section: Resultsmentioning

confidence: 99%

Synthesis of New Glycosylated Flavonoids with Inhibitory Activity on Cell Growth

et al. 2018

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“…Despite the presence of protective groups, some of the glycosyl bromides undergo hydrolysis, which is why the glycosylation reaction in some cases must be carried out in additionally dehydrated solvents and the presence of a water adsorbent, for example, molecular sieves ( Needs and Williamson, 2001 ; Smith et al, 2006 ; Mei et al, 2015 ). Moreover, some authors note the appearance in the reaction mixture of side products—glycals ( Needs and Williamson, 2001 ; Reszka et al, 2020 ).…”

Section: Donors Of Glycosidic Groupsmentioning

confidence: 99%

“…The reaction between the flavanone derivatives and 2,3,4,6-tetra-O-acetyl-a-D-glucopyranosyl bromide was carried out in a mixture of quinoline and benzene. In later works, glycosylation was carried out in pure quinoline ( Zemplén et al, 1943 ), pyridine ( Hörhammer et al, 1966 ), chloroform with the addition of a desiccant ( Maloney and Hecht, 2005 ; Smith et al, 2006 ), and freshly distilled dichloromethane ( Mei et al, 2015 ). The reaction has been used to glycosylate flavanones, chalcones, and flavonols, respectively.…”

Section: Flavonoid Glycosylation Reactionsmentioning

confidence: 99%

Progress and Achievements in Glycosylation of Flavonoids

et al. 2021

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In recent years, the chemistry of flavonoid glycosylation has undergone significant developments. This mini-review is devoted to summarizing existing strategies and methods for glycosylation of natural and synthetic flavonoids. Herein we overviewed the reaction conditions of flavonoid glycosylation depending on the position of hydroxyl groups in a parent molecule, the degree of it conjugation with the π-system, the presence of steric factors, the formation of intramolecular hydrogen bonds, etc. Especial attention was given to the choice of the glycosyl donor moiety, which has a significant effect on the yield of the final glycosidated products. Finally, a general strategy for regioselective glycosylation of flavonoids containing several hydroxyl groups is outlined.

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“…Yang 等 [48,49] 以山萘酚为原料, 合成了系列山萘酚 3-O-糖苷和山萘酚 3,7-二糖苷化合物. 山奈酚衍生物是淫羊藿苷具有良好抗肿瘤活性的黄酮苷元, 文献报道 [50] , 以山奈酚为原料, 经过 11 个线性步骤半合成了淫羊藿苷, 总收率为 7%. [51] .…”

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Advances on Synthesis of Flavonoid Glycosides

Xu¹,

Li²,

Wu³

et al. 2019

Chin. J. Org. Chem.

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Flavonoid glycoside is commonly found in natural plants, possesses diverse bioactivities and potential medicinal values, and its synthesis methods are worthy to be studied. The synthesis of flavonoid glycosides covering the literatures from 2014 to 2018 is reviewed. The flavonoid glycoside synthesis includes two major methods of chemosynthesis and biosynthesis. Chemosynthesis includes total synthesis and semi-synthesis. The total synthesis has two classical methods of the Baker-Venkataraman (BK-VK) reaction and the Algar-Flynn-Oyamada (AFO) reaction. The semi-synthesis is usually starting from natural flavonoid, such as rutin, quercetin, kaempferol, naringenin and so on. Moreover, the chemosynthesis of flavonoid O-glucoside has three prime methods, Koening-Knorr method, phase transfer catalysis method, and glycosyl trichloroacetimidate method. As for the chemosynthesis of flavonoid C-glycoside, its glycosidic linkage is mainly completed via the O→C rearrangement reaction. Currently, the glycosyltransferase and glycosynthase are usually employed in the enzyme-catalyzed biosynthesis of flavonoid glycosides.

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Synthesis of icariin from kaempferol through regioselective methylation and para-Claisen–Cope rearrangement

Cited by 24 publications

References 31 publications

Synthesis of New Glycosylated Flavonoids with Inhibitory Activity on Cell Growth

Synthesis of New Glycosylated Flavonoids with Inhibitory Activity on Cell Growth

Progress and Achievements in Glycosylation of Flavonoids

Advances on Synthesis of Flavonoid Glycosides

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