Photochemical transformation of 20-hydroxyecdysone: production of monomeric and dimeric ecdysteroid analogues

Harmatha, Juraj; Budêšínský, Miloś; Vokáč, Karel

doi:10.1016/s0039-128x(01)00140-4

Cited by 34 publications

(17 citation statements)

References 10 publications

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“…The 13 C NMR spectrum of compound 5 agrees with the spectrum of the previously obtained by photochromic transformation of the 20-hydroxyecdysone to 14α-hydroperoxy-20-hydroxyecdysone [8]. The 13 C NMR spectra of compounds 6-8 were similar to that of the 14α-hydroxyperoxide 5.…”

supporting

confidence: 81%

“…The 13 C NMR spectra of compounds 6-8 were similar to that of the 14α-hydroxyperoxide 5. The shift of the C-14 signal to low field (∆δ ~ 11 ppm) is typical for the 13 C NMR spectra of hydroperoxides [3,8]. The structure of compound 13 was proved from 1 H NMR and 13 C NMR spectroscopic data by a combination of 1D and 2D procedures.…”

mentioning

confidence: 99%

“…It has been reported that a compound similar to compound 20 but with free hydroxyl groups, is formed upon photolysis of 20-hydroxyecdysone [3]. However, it was then shown that this stable in air compound was the dimer of the ∆ 8(14) analog [8]. The structure of compound 20 was proved from the 1D and 2D 1 H and 13 C NMR spectra (HHCOSY, HSQC, HMBC, and NOESY).…”

mentioning

confidence: 99%

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Novel ecdysteroid analogs with oxygen-containing heterocycles in the steroid skeleton

Odinokov

Galyautdinov

Ibragimova

et al. 2008

Chem Heterocycl Comp

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The reaction of ecdysteroids (20-hydroxyecdysone and its acetonides) with lithium in liquid ammonia gave novel analogs with an oxetane 9α,14α-oxacycle in the steroid skeleton. In aqueous alcohol solution the 9,14-oxa analogs rearrange to the more stable 9α,13α−oxa analogs through a 1,2-migration of the 18-Me group from the C-13 to the C-14 atom.Although widely used in the chemistry of steroids [1, 2] for the selective reduction of a double bond in conjugated enones, a reaction with alkali metals in liquid ammonia has been little studied amongst the series of ecdysteroids. It is only known that the reaction of 20-hydroxyecdysone diacetonide with lithium in liquid ammonia solution gives a 14α-hydroperoxy derivative rather than the corresponding 7,8-dihydro analog [3].We have found that the action of a solution of lithium in liquid ammonia on the ecdysteroids 20-hydroxyecdysone (1), its 2,3:20,22 diacetonide (2), and the 20,22-acetonide (3) and 2,3-acetonide (4) and subsequent treatment of the reaction mixture with NH 4 Cl gives the corresponding 14α-hydroperoxides 5-8 together with the previously unknown 9α,14α-oxa derivatives 9-12 which are analogs of ecdysteroids with an oxetane ring in the steroid skeleton (Scheme 1). In the case of compound 1 the corresponding oxetane 9 and 14α-hydroperoxide 5 are formed in approximately equimolar amounts while the acetonides 2 and 3 are primarily converted to the corresponding oxetanes 10 and 11. For the 2,3-acetonide 4 the oxetane formed 12 is less stable than oxetanes 9-11 and elution of reaction products (SiO 2 , MeOH/CHCl 3 , 1:50) gave a mixture of the oxetane 12 and its isomerization product 19 as well as a mixture of the 14α-hydroperoxide 12 and starting material 4. Repeated chromatography (SiO 2 , MeOH/CHCl 3 ) of a mixture of compounds 12 and 19 gave the individual forms of the transformation products of oxetane 12, i.e. compounds 15 and 19.

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confidence: 99%

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confidence: 99%

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Novel ecdysteroid analogs with oxygen-containing heterocycles in the steroid skeleton

Odinokov

Galyautdinov

Ibragimova

et al. 2008

Chem Heterocycl Comp

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“…14-Deoxy-20-hydroxyecdysone (14d20E) was initially prepared from 20E by phototransformation [22] and later according with the procedure of Zhu et al [23]. Poststerone and 14-deoxypoststerone were prepared from 20E and 14d20E using a side-chain cleavage method described by Petersen et al [24].…”

Section: Synthesis Of Reference Ecdysteroidsmentioning

confidence: 99%

The metabolism of 20-hydroxyecdysone in mice: Relevance to pharmacological effects and gene switch applications of ecdysteroids

Kumpun

Girault

Dinan

et al. 2011

The Journal of Steroid Biochemistry and Molecular Biology

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“…It was reported [2,3] that Δ 8(14) -14α-deoxy-20-hydroxyecdysone formed at the photochemical transformation of 20-hydroxyecdysone (35% in a mixture with the other compounds), but this data were not confi rmed [4].…”

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confidence: 92%

Δ8(14)-14α-deoxy- and 14α-deoxy-14α-hydroperoxyecdysteroids

et al. 2010

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Photochemical transformation of 20-hydroxyecdysone: production of monomeric and dimeric ecdysteroid analogues

Cited by 34 publications

References 10 publications

Novel ecdysteroid analogs with oxygen-containing heterocycles in the steroid skeleton

Novel ecdysteroid analogs with oxygen-containing heterocycles in the steroid skeleton

The metabolism of 20-hydroxyecdysone in mice: Relevance to pharmacological effects and gene switch applications of ecdysteroids

Δ8(14)-14α-deoxy- and 14α-deoxy-14α-hydroperoxyecdysteroids

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