<b>Vinca Alkaloids. X<sup>1</sup>. The Structure of Vindoline</b>

Gorman, Marvin; Neuss, Norbert; Biemann, K.

doi:10.1021/ja00865a042

Cited by 108 publications

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“…Since this oxidation has no effect on C(15 ), in impurity A the C(15 ) OH group should be in the ␣ position as in vincadioline. This was confirmed on the basis of 1D 1 H, 13 C and 2D NOESY, ROESY, HSQC, HMBC and TOCSY measurements for C(15 ) OH VCR on our 800 MHz NMR spectrometer [46]. The relatively small (<2 Hz) coupling between H-14 and H-15 , the OH substituent effect on the ␥-carbons C(3 ), C (19 ) and C (21 ), and the 2D NOE pattern concluded that the hydroxyl group is in the ␣ position at C(15 ) in this VCR derivative.…”

Section: Historical Examples Of Bisindole Structure Identification Bysupporting

confidence: 54%

“…Fragment B (m/z 355) corresponds to the velbanamine part of the molecule. Fragment m/z 282, which is a characteristic fragment of the vindoline part, was rationalized by the structure E [13,14,16]. A Retro Diels-Alder fragmentation (G) can also be observed for VLB resulting in the fragment at m/z 650 (m/z 651 is more intense in the mass spectrum).…”

Section: Ei-ms Analysismentioning

confidence: 97%

“…4), a major alkaloid of C. roseus [13][14][15][16] and a building block of bisindole alkaloids. A comparative mass spectrometric study suggested that vindoline possesses an aspidospermine skeleton.…”

Section: Ei-ms Analysismentioning

confidence: 99%

“…1) in different solvents [67]. In this work, the complete 1 H, 13 C and 15 N NMR assignment of both the base and of the salt form of vinorelbine was achieved on the basis of 1 H, 13 C, COSY, NOESY, and heterocorrelation experiments on a 400 MHz spectrometer. Besides the chemical shift assignments, a detailed conformational study was performed on the basis of chemical shift considerations, coupling constant analysis and NOE intensities.…”

Section: Conformational Aspects Of Vlb Analoguesmentioning

confidence: 99%

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Structure elucidation of indole–indoline type alkaloids: A retrospective account from the point of view of current NMR and MS technology

Béni¹,

Háda²,

Dubrovay³

et al. 2012

Journal of Pharmaceutical and Biomedical Analysis

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Section: Historical Examples Of Bisindole Structure Identification Bysupporting

confidence: 54%

Section: Ei-ms Analysismentioning

confidence: 97%

Section: Ei-ms Analysismentioning

confidence: 99%

Section: Conformational Aspects Of Vlb Analoguesmentioning

confidence: 99%

See 2 more Smart Citations

Structure elucidation of indole–indoline type alkaloids: A retrospective account from the point of view of current NMR and MS technology

Béni¹,

Háda²,

Dubrovay³

et al. 2012

Journal of Pharmaceutical and Biomedical Analysis

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“…The metabolite lb behaved much like vindoline in the mass spectrometer (6), and fragmentation pathways important to the assignment of the structure of lb are shown in Fig. 2 …”

Section: Methodsmentioning

confidence: 99%

Microbial Transformations of Natural Antitumor Agents: O -Demethylation of Vindoline by Sepedonium chrysospermum

Nabih

Youel

et al. 1978

Antimicrob Agents Chemother

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Vindoline (la) was transformed to O-demethylvindoline (lb) by Sepedonium chrysospermum ATCC 13378 in 33% yield. Thin-layer and high-pressure liquid chromatographic methods distinguished lb from previously reported microbial metabolites of vindoline. The structural proof of lb was based on its mass spectral fragmentation pattern and on its chemical and nuclear magnetic resonance spectral properties.The Vinca alkaloids vincristine and vinblastine possess significant antitumor activity and are widely used clinically. They have resisted simple syntheses, and their structural complexity has hindered the preparation of other useful derivatives of the alkaloids by chemical methods. Microbial transformations are being examined for their potential to prepare potentially important Vinca alkaloid derivatives.Vindoline (la) is one of the monomeric Vinca alkaloids and one of the most abundant alkaloids in Vinca rosea L. Since it is more readily available than vincristine and vinblastine, it was used in an effort to identify new types of biotransformation products of this group of alkaloids. Previous reports document the production of a variety of metabolites of vindoline by streptomycetes. Known vindoline metabolites include ( Fig. 1): deacetylvindoline (Ic) and deacetyldihydrovindoline ether (2c) (9); dihydrovindoline ether (2a); 3-acetonyldihydrovindoline ether (2b); a ring contraction product known as 16-dehydroxy-14,15-epoxy-14-oxo-3-norvindoline (12); N-demethylvindoline (Id) (13); and a dimer consisting of two dihydrovindoline ether moieties linked through their 3 and 14 positions (11).This report describes selective cleavage of the methyl ether group of vindoline by Sependonium chrysospermum ATCC 13378. The reaction gives lb in 33% yields, and it is not complicated by the formation of other side products. MATERIALS AND METHODSMelting points were determined on a Thomas-Hoover apparatus and are uncorrected. Infrared spectra were determined on a Perkin-Elmer 267 grating infrared spectrophotometer. Nuclear magnetic resonance (NMR) spectra were determined on a VarianAssociates model T-60 spectrometer using tetramethylsilane as an internal standard. Low-resolution mass spectra were obtained on a Finnigan model 3200 spectrometer, and high-resolution mass spectral data were provided by the Department of Chemistry, Massachusetts Institute of Technology, Cambridge. UV spectra were obtained on a Beckman DK-2 instrument. Elemental analyses were determined by Integral Microanalytical Laboratories, Inc., Raleigh, N.C.Vindoline, deacetylvindoline, dihydrovindoline ether, N-demethylvindoline, 3-acetonyldihydrovindoline ether, and 16-dehydroxy-14,15-epoxy-14-oxo-3-norvindoline were obtained as authentic reference standards from Eli Lilly and Co., Indianapolis, Ind.The purity of each compound was verified by thinlayer chromatography (TLC), high-pressure liquid chromatography, and mass spectral analysis. Vindoline (7) dihydrovindoline ether and the dihydrovindoline ether dimer (11) were characterized by melting points and UV, NMR, and...

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Alkaloids

Mascavage

Jasmin

Sonnet

et al. 2010

Ullmann's Encyclopedia of Industrial Chemistry

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The article contains sections titled: 1. Introduction 2. Alkaloids Derived from Polyketides and the Amino Acids Ornithine and Lysine 2.1. Alkaloids Derived by the Insertion of Nitrogen into a Polyketide 2.1.1. ( S )‐(+)‐Coniine, γ‐Coniceine and Related Alkaloids 2.1.2. Solenopsin Family (Fire Ant Alkaloids) 2.1.3. Perhydroazaphenalenes: Defensive Alkaloids of the Coccinellidae 2.1.4. Cyanobacteria Alkaloids 2.1.5. Additional Polyketide‐Derived Alkaloids 2.2. Alkaloids Derived from Ornithine and/or Arginine 2.2.1. Tropane Alkaloids 2.2.2. Pyrrolizidine Alkaloids 2.3. Alkaloids Derived from Ornithine (and/or Arginine) and Nicotinic Acid 2.4. Alkaloids Derived from Lysine (Lys, K) and Nicotinic Acid 2.5. Purine Alkaloids 2.6. Imidazole Alkaloids 2.7. Pepper Alkaloids 3. Alkaloids Derived from the Shikimate Pathway 3.1. Alkaloids Derived from Anthranilate 3.2. Alkaloids Derived from Phenylalanine and Tyrosine 3.2.1. Biosynthesis of Dopamine, Mescaline and Capsaicin 3.2.2. Biosynthesis of Tetrahydroisoquinoline Alkaloids 3.2.3. Cryptostyline (Orchidaceae) and Alkaloids of the Amaryllidaceae 3.2.4. Ephedra Alkaloids 3.3. Alkaloids Derived from Tyrosine 3.4. Alkaloids Derived from Tryptophan and/or Tryptamine (Indole Alkaloids) 3.4.1. Alkaloids Derived from Tryptamine and an Unrearranged Monoterpene Unit 3.4.2. Mold Metabolites 3.4.3. Ergot Alkaloids 3.4.4. Corynantheine–Heteroyohimbine Structural Types 3.4.5. Corynantheine‐Type Alkaloids 3.4.6. Ajmalicine‐Type Alkaloids 3.4.7. Heteroyohimbine Oxindole Type 3.4.8. Glucoalkaloids 3.4.9. Yohimbine–Reserpine Structural Types 3.4.10. Akuammidine–Quebrachidine–Ervatamine–Gelsemine–Akuammiline Structural Types 3.4.11. Uleine–Ellipticine–Vallesamine–Ngouniensine Structural Types 3.5. The Cinchona Structural Type 3.6. The Camptothecin Structural Type 3.7. Terpene, Sesquiterpene, Diterpene and Steroidal Alkaloids (→ ((anchor interlink a26_205.xml Terpenes))) 3.7.1. Overview of Terpenoid Biosynthesis 3.7.2. Monoterpene Alkaloids 3.7.3. Sesquiterpene Alkaloids 3.7.4. Diterpene Alkaloids 3.7.5. Sesterterpene and Triterpene Alkaloids 3.7.6. Steroidal Alkaloids 4. Summary

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Vinca Alkaloids. X¹. The Structure of Vindoline

Cited by 108 publications

References 0 publications

Structure elucidation of indole–indoline type alkaloids: A retrospective account from the point of view of current NMR and MS technology

Structure elucidation of indole–indoline type alkaloids: A retrospective account from the point of view of current NMR and MS technology

Microbial Transformations of Natural Antitumor Agents: O -Demethylation of Vindoline by Sepedonium chrysospermum

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Vinca Alkaloids. X1. The Structure of Vindoline

Cited by 108 publications

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Structure elucidation of indole–indoline type alkaloids: A retrospective account from the point of view of current NMR and MS technology

Structure elucidation of indole–indoline type alkaloids: A retrospective account from the point of view of current NMR and MS technology

Microbial Transformations of Natural Antitumor Agents: O -Demethylation of Vindoline by Sepedonium chrysospermum

Alkaloids

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Vinca Alkaloids. X¹. The Structure of Vindoline