First Conjugates of the Diterpenoid Isosteviol and Glucuronic Acid

Andreeva, O. V.; Sharipova, R. R.; Strobykina, I. Yu.; Катаев, В. Е.

doi:10.1007/s10600-014-0988-7

Cited by 8 publications

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References 20 publications

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“…Recently the first syntheses of open chain and macrocyclic glycoterpenoids having one or several diterpenoid moieties bonded with various carbohydrate residues, namely D-glucopyranose [1,2] , glucuronic acid [3][4][5] or trehalose [6,7] have been reported. In continuation of these investigations 2-deoxy-2-amino-D-glucopyranose (glucosamine) was chosen as the next carbohydrate block for macrocyclic glycoterpenoids.…”

Section: Introductionmentioning

confidence: 99%

Last Step towards Macrocyclic Glycoterpenoids Having Isosteviol and Glucosamine Moieties

Garifullin¹,

Strobykina²,

Sharipova³

et al. 2016

MHC

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Section: Introductionmentioning

confidence: 99%

Last Step towards Macrocyclic Glycoterpenoids Having Isosteviol and Glucosamine Moieties

Garifullin¹,

Strobykina²,

Sharipova³

et al. 2016

MHC

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Synthesis of a Macrocyclic Conjugate of the Diterpenoid Isosteviol and Glucuronic Acid

et al. 2015

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A macrocyclic conjugate of the natural diterpenoid isosteviol (16-oxo-ent-beyeran-19-oic acid) and glucuronic acid was synthesized for the first time. The conjugate contained two molecules of dihydroisosteviol E-D-glucuronoside joined by 1, 8-octanedicarboxylate and 1,8-octanedicarbazoyl spacers. We recently reported the synthesis of the first conjugate of the diterpenoid isosteviol (16-oxo-ent-beyeran-19-oic acid) and glucuronic acid [1] in which two molecules of the isosteviol derivative dihydroisosteviol (16-hydroxy-ent-beyeran-19-oic acid) functionalized at the carboxyls by E-D-glucopyranuronoyl residues were connected by a 1,6-hexanedicarboxylate spacer. In continuation of research on the synthesis of macrocyclic glycoterpenoids [2], herein we present results for the synthesis of a macrocyclic conjugate of isosteviol and glucuronic acid. We used the methodology for synthesizing macrocyclic isosteviol derivatives [3,4] in which two dihydroisosteviol molecules were first bound through the hydroxyls by reacting them with carboxylic acid chlorides. The resulting diacids (e.g., diacid 4 in Scheme 1) were converted to macrocycles by reacting their carboxylic acid chlorides with diols.The starting carbohydrate component was D-(+)-glucurono-3,6-lactone (1), which was easily converted to methyl-1,2,3,4-tetra-O-acetyl-E-D-glucopyranuronate (2) as before [5]. The methyl-1-deoxy-1-bromo-2,3,4-tri-O-acetyl-E-Dglucopyranuronate 3 that was obtained from it by the literature method [6] was then reacted with diacid 4 in refluxing CH 2 Cl 2 in the presence of tetrabutylammonium bromide (TBAB) and potash. Bisglucuronide 5 was obtained in 56% yield. Its anomeric protons appeared in the PMR spectrum as a single doublet at 5.73 ppm with vicinal SSCC 8.02 Hz. This indicated convincingly that the glycoside bonds had the E-orientation.In fact, the anomeric proton of methyl 1,2,3,4-tetra-O-acetyl-E-D-glucopyranuronate 2 resonated as a doublet at 5.73 ppm with vicinal SSCC 7.8 Hz [6] whereas the anomeric proton of the corresponding D-D-glucopyranuronate was found as a doublet at 6.34 ppm with SSCC 3.7 Hz [5]. Then, bisglucuronoside 5 was reacted at room temperature with hydrazine hydrate as before [7]. The PMR spectrum of the product, which was obtained in 90% yield, lacked the strong singlets corresponding to acetate resonances at 1.96, 1.98, and 1.99 ppm and the ester methyls of the glucopyranuronates at 3.68 ppm, which were observed in the spectrum of 5. A multiplet that was characteristic of the hydrazide NH proton appeared at 7.69-7.73 ppm. All these data combined with MALDI mass spectral data indicated that dihydrazide 6 had formed. The reaction did not affect the carbohydrate anomeric centers. Therefore, the glycoside bonds in 6 retained the E-orientation. Its glucuronate anomeric protons resonated as a single doublet at 3.78 ppm with SSCC 9.63 Hz, which agreed with the literature for various E-glycosides of non-acylated glucuronic acid methyl ester (e.g., G 4.26 ppm and 3 J = 9.4 Hz [8]) and with previous work [9] in whic...

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Synthesis and Antimicrobial and Antituberculosis Activity of the First Conjugates of the Diterpenoid Isosteviol and D-Arabinofuranose

et al. 2018

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First Conjugates of the Diterpenoid Isosteviol and Glucuronic Acid

Cited by 8 publications

References 20 publications

Last Step towards Macrocyclic Glycoterpenoids Having Isosteviol and Glucosamine Moieties

Last Step towards Macrocyclic Glycoterpenoids Having Isosteviol and Glucosamine Moieties

Synthesis of a Macrocyclic Conjugate of the Diterpenoid Isosteviol and Glucuronic Acid

Synthesis and Antimicrobial and Antituberculosis Activity of the First Conjugates of the Diterpenoid Isosteviol and D-Arabinofuranose

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