The structure of codonopsine

Matkhalikova, C. F.; Malikov, V. M.; Yunusov, S. Yu.

doi:10.1007/bf00568618

Cited by 14 publications

(23 citation statements)

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“…The isolation of the alkaloids codonopsine (1) and codonopsinine (2) from the aerial part of Codonopsis clematidea (harebell, Campanulaceae) has been previously reported [1]. Based on spectral data (IR, UV, NMR, and mass spectroscopy) and chemical transformations (Hofmann degradation, KMnO 4 and periodic-acid oxidation), the structures for 1 and 2 were established as 1,2-dimethyl-3,4-dihydroxy-5-(3,4-dimethoxyphenyl)pyrrolidine and 1,2-dimethyl-3,4-dihydroxy-5-(4methoxyphenyl)pyrrolidine, respectively [2,3].…”

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Stereochemistry of the alkaloids codonopsine and codonopsinine

et al. 2004

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The isolation of the alkaloids codonopsine (1) and codonopsinine (2) from the aerial part of Codonopsis clematidea (harebell, Campanulaceae) has been previously reported [1]. Based on spectral data (IR, UV, NMR, and mass spectroscopy) and chemical transformations (Hofmann degradation, KMnO 4 and periodic-acid oxidation), the structures for 1 and 2 were established as 1,2-dimethyl-3,4-dihydroxy-5-(3,4-dimethoxyphenyl)pyrrolidine and 1,2-dimethyl-3,4-dihydroxy-5-(4methoxyphenyl)pyrrolidine, respectively [2, 3]. Later double-resonance PMR spectroscopy was used in an attempt to determine the relative configuration of the substituents on the N-methylpyrrolidine ring [4].The methyl iodide of codonopsine (3) was prepared and its x-ray crystal structure was solved in order to solve unambiguously these issues.The results of the x-ray structure analysis (XSA) confirm the proposed chemical formulas for 1 and 2 [2, 3] but necessitate a correction in the stereochemistry of the N-methylpyrrolidine ring. Figure 1 shows the corrected structural formulas for 1 and 2 and the molecular structure of codonopsine methyl iodide (3).It can be seen that the C2 methyl and the C4 hydroxyl have the α-configuration; the C3 hydroxyl and the C5 substituted aromatic ring, the β-configuration. The N-methylpyrrolidine ring adopts the 5α-envelope conformation. Atom C5 deviates from the plane of the other four atoms (coplanar within ±0.027 Å) by 0.625 Å. For this reason, only C4 and C5 can have substituents that are pseudo-axial or -equatorial relative to the plane of the four atoms. The C4 hydroxyl and C5 aromatic ring are pseudo-equatorial. The planar (±0.01 Å) substituted aromatic ring is twisted relative to the plane of the pyrrolidine ring by 74.2°.The absolute configuration of 3 was also established from the XSA. According to the Flack parameter [5] [0.00(4)], the absolute configuration of the chiral centers corresponds with that shown in Fig. 1. Therefore, all asymmetric centers (C2, C3, C4, and C5) have the R-configuration.

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Stereochemistry of the alkaloids codonopsine and codonopsinine

et al. 2004

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“…[19] Compared to DMDP, the β--fructosyl derivative 13 had markedly lower inhibitory activity toward β-galactosidases but enhanced inhibitory potential toward porcine kidney trehalase (IC 50 = 26 µ) by about 10-fold. The novel pyrrolizidine, 3-epicasuarine (14), was also recently isolated from Myrtus communis by Fleet and co-workers. [20] 3-epi-Casuarine was found to have a different biological profile to that of casuarine -as illustrated by its ability to inhibit almond β-glucosidase to a greater extent than the α-glucosidases tested.…”

Section: Natural Occurrence Of Pyrrolidine-containing Iminosugarsmentioning

confidence: 96%

“…[13] Its biological activity is the least studied of the three primary structures. Other notable pyrrolidines include codonopsine (5) and codonopsinine (6), first isolated in 1969 from Codonopsis clematidea, [14] and the radicamines A (7) and B (8), recently isolated from Lobelia chinensis LOUR. [15] Of the bicyclic pyrrolidine-containing iminosugars, representative examples include the pyrrolizidine casuarine (9), [16] and the indolizidine swainsonine (10), the first bicyclic alkaloid to be discovered.…”

Section: Natural Occurrence Of Pyrrolidine-containing Iminosugarsmentioning

confidence: 99%

“…Of particular note during the last few years has been the role of chemical synthesis to resolve the absolute stereochemistry of several iminosugars. Since their isolation in 1969, [14] the stereochemistry of codonopsine and codonopsinine has been in question. To resolve these issues, the methyl iodide of codonopsine was prepared and the X-ray crystal structure solved.…”

Section: Natural Occurrence Of Pyrrolidine-containing Iminosugarsmentioning

confidence: 99%

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Recent Developments in the Synthesis of Pyrrolidine‐Containing Iminosugars

et al. 2010

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As noted inhibitors of glycosidases, iminosugars have enormous therapeutic potential in the treatment of a number of diseases such as cancer, diabetes, and lysosomal storage disorders. Accordingly, much effort has been expended over the past decades in developing novel and efficient methodologies for the synthesis of iminosugars. This microreview highlights recent (post 2005) developments in the synthesis of pyrrolidine‐containing iminosugars and includes discussions of methodologies such as ring‐closing metathesis, aldol and pericyclic reactions, and protecting‐group free strategies.

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“…These simple procedures allow for the facile synthesis of various E-and Zconfigured anti-amino allylic alcohols and thus offer a unique opportunity for rapidly constructing the structural and stereochemical frameworks of poly-functionalized molecules. Indeed, (E)-8 and (Z)-8 were effectively transformed into (À)-codonopsinine (6 a) [19][20][21] and (À)-2-epi-codonopsinine (6 b), [20b,c] respectively, where the olefin geometry of 8 was reflected in the C2 stereochemistry of the pyrrolidine skeleton. To the best of our knowledge, this is the first example of a catalytic asymmetric synthesis of these pyrrolidine alkaloids, which exhibit antibiotic and hypotensive activities without affecting the central nervous system.…”

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confidence: 99%