Synthesis of Deuterium Labeled Silybin and Isosilybin

Ferenczi, Renáta; Kurtán, Tibor; Dinya, Zoltán; Antus, Sándor

doi:10.1515/hc.2005.11.6.491

Cited by 3 publications

(4 citation statements)

References 7 publications

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“…A good regioselectivity of esterication can be achieved with some long chain carboxylic acids (Table 6). Acylation with acyl chlorides under basic conditions (pyridine) yielded C-7 acyl derivatives (63-69), whereas the use of a Lewis acid (BF 3 ) as the promoter gave C-23 (70)(71)(72)(73)(74)(75)(76)(77)(78) esters in overall yields of ca. 40%.…”

Section: Aliphatic and Olenic Estersmentioning

confidence: 99%

“…To enable the detailed mass spectroscopic investigation of silybin, Ferenczi et al 71 developed a synthesis of deuteriumlabeled silybin. The synthesis is based on Merlini's biomimetic synthesis of silybin 36 (Scheme 2) and uses Ag 2 O for coupling of a deuterated coniferyl alcohol (119) with taxifolin (1g) to obtain the diastereomeric mixtures of deuterated silybin (120) and deuterated isosilybin (121, Scheme 8).…”

Section: Isotopic Labeling Of Silybinmentioning

confidence: 99%

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Chemistry of silybin

et al. 2014

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Silybin, a secondary metabolite isolated from the seeds of the blessed milk thistle (Silybum marianum) was discovered as the first member of a new family of natural compounds called flavonolignans in 1959. Over the years it has received the research attention of many organic chemists. This research has resulted in a number of semisynthetic derivatives prepared in an effort to modulate and better target the biological activities of silybin or to improve its physical properties, such as its solubility. A fundamental breakthrough in silybin chemistry was the determination of the absolute configurations of silybin A and silybin B, and the development of methods for their separation. This review covers articles dealing with silybin chemistry and also summarizes all the derivatives prepared.

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Section: Aliphatic and Olenic Estersmentioning

confidence: 99%

Section: Isotopic Labeling Of Silybinmentioning

confidence: 99%

Chemistry of silybin

et al. 2014

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“…rac ‐3,5,7‐Trihydroxy‐2‐phenyl‐4‐chromanone ( 3 ) and 2‐(1,4‐benzodioxolanyl)‐3,5,7‐trihydroxy‐4‐chromanone ( 4 ) were prepared according to the method described by Takahashi et al 23. The synthesis of (+)‐deuterosilybin ( 2 ) is given in Ferenczi et al 24. The compounds were characterized by 1 H‐NMR, 13 C‐NMR and IR spectroscopy.…”

Section: Methodsmentioning

confidence: 99%

(+)‐Silybin, a pharmacologically active constituent of Silybum marianum: fragmentation studies by atmospheric pressure chemical ionization quadrupole time‐of‐flight tandem mass spectrometry

Kéki¹,

Tóth²,

Zsuga³

et al. 2007

Rapid Comm Mass Spectrometry

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The fragmentation behavior of (+)-silybin (1) and (+)-deuterosilybin (2), as well as of their flavanone-3-ol-type building blocks, such as 3,5,7-trihydroxy-2-phenyl-4-chromanone (3) and 2-(1,4-benzodioxolanyl)-3,5,7-trihydroxy-4-chromanone (4), were investigated by atmospheric pressure chemical ionization quadropole time-of-flight tandem mass spectrometry in the positive ion mode (APCI(+)-QqTOF MS/MS). The product ion spectra of the protonated molecules of 1 revealed a rather complicated fragmentation pattern with product ions originating from consecutive and competitive loss of small molecules such as H2O, CO, CH2O, CH3OH and 2-methoxyphenol, along with the A+- and B+-type ions arising from the cleavage of the C-ring of the flavanone-3-ol moiety. The elucidation of the fragmentation behavior of 1 was facilitated by acquiring information on the fragmentation characteristics of the flavanone-3-ol moieties and 2. The capability of the accurate mass measurement on the quadrupole time-of-flight mass spectrometer allowed us to determine the elemental composition of each major product ion. Second-generation product ion spectra obtained by combination of in-source collision induced dissociation (CID) with selective CID (pseudo-MS(3)) was also helpful in elaborating the fragmentation pathways and mechanism. Based on the experimental results, a fragmentation mechanism as well as fragmentation pathways for 1 and its flavanone-3-ol building blocks (3, 4) are proposed and discussed.

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“…12 Recently, the lipase from Pseudomonas fluorescens (PsfL)-catalyzed kinetic resolution of 2-hydroxymethyl-1,4-benzodioxanes was considered a convenient method for the resolution of their enantiomers. [13][14][15][16][17][18] As a continuation of our ongoing research on the synthesis of naturally occurring flavanolignans possessing 1,4-benzodioxane moiety and significant hepatoprotective activity, 19,20 it seemed promising to use this method for the preparation of dextrorotatory enantiomers of 1,4-benzodioxane 6-or 7 carbaldehyde derivatives (3, 4), which may serve as suitable building blocks for the synthesis of hepatoprotective (2S,2'R,3'R)-silandrin (1) and (2S,2'R,3'R)-isosilandrin (2), respectively, isolated from the white-flowered variant of Silybum marianum. 21,22 (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Kinetic resolution of 2-hydroxymethyl-1,4-benzodioxanes by Pseudomonas fluorescens

Kónya¹,

Ferenczi²,

Czompa³

et al. 2008

Arkivoc

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Pseudomonas fluorescens lipase-catalyzed transesterification of 2-hydroxymethyl-1,4-benzodioxanes of different substitution patterns were studied in the presence of vinyl acetate in organic solvents. The influence of structural features on the conversion and enantioselectivity is discussed and it is shown that the presence of a C-3 methyl or aryl substituent significantly hinders the binding of the substrate to the active site of the enzyme. Thus, with a bulky C-3 substituent no transesterification of the 2-hydroxymethyl group could be observed.

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Synthesis of Deuterium Labeled Silybin and Isosilybin

Cited by 3 publications

References 7 publications

Chemistry of silybin

Chemistry of silybin

(+)‐Silybin, a pharmacologically active constituent of Silybum marianum: fragmentation studies by atmospheric pressure chemical ionization quadrupole time‐of‐flight tandem mass spectrometry

Kinetic resolution of 2-hydroxymethyl-1,4-benzodioxanes by Pseudomonas fluorescens

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