Efficient synthesis of α,β-unsaturated γ-lactones linked to sugars

Rauter, Amélia P.; Figueiredo, José A.; Ismael, Maria I.; Canda, Tana; Font, Josep; Figueredo, Marta

doi:10.1016/s0957-4166(01)00197-5

Cited by 51 publications

(58 citation statements)

References 35 publications

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“…6 Compounds with this feature appear throughout the plant kingdom from the simple metabolites of lichens and fungi to the sesquiterpenes and steroidal glycosides, having also been found in animal species such as sponges, butterflies, and insects. 7 Some of these compounds have been described as potential anticancer agents, phospholipase A2 and cyclooxygenase inhibitors. 1 Electrospray ionization mass spectrometry (ESI-MS) is one of the techniques of choice for the analysis of non-volatile and thermally labile compounds.…”

mentioning

confidence: 99%

Electrospray ionization mass spectrometric analysis of newly synthesized α,β‐unsaturated γ‐lactones fused to sugars

Madeira

Rosa

Xavier

et al. 2010

Rapid Comm Mass Spectrometry

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Knowledge of the fragmentation mechanisms of lactones and their behaviour under electrospray ionization (ESI) conditions can be extended to larger and more complex natural products that contain an alpha,beta-unsaturated gamma-lactone moiety in their structure. Moreover, little is known about the gas-phase behaviour of alpha,beta-unsaturated gamma-lactones linked or fused to sugars. Therefore, five alpha,beta-unsaturated gamma-lactones (butenolides) fused to a pyranose ring, recently synthesized compounds with potential relevance regarding their biological properties, were investigated using ESI-MS and ESI-MS/MS in both positive and negative ion modes. Their fragmentation mechanisms and product ion structures were compared. It was observed that two isomers could be unambiguously distinguished in the negative ion mode by the fragmentation pathways of their deprotonated molecules as well as in the positive ion mode by the fragmentation pathways of either the protonated or the sodiated molecule. Fragmentation mechanisms are proposed taking into account the MS/MS data and semi-empirical calculations using the PM6 Hamiltonean. The semi-empirical calculations were also very useful in determining the most probable protonation and cationization sites.

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confidence: 99%

Electrospray ionization mass spectrometric analysis of newly synthesized α,β‐unsaturated γ‐lactones fused to sugars

Madeira

Rosa

Xavier

et al. 2010

Rapid Comm Mass Spectrometry

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“…The MS 3 spectrum of the m/z 239.07 (Fig. 2c) shows that this ion loses CO affording the m/z 211.08 ion, which subsequently can lose another CO (confirmed by MS 3 , Fig. 2d) affording the ion at m/z 183.08.…”

Section: Protonated Compounds 1 Andmentioning

confidence: 83%

“…[1,2] Compounds with lactones of this type appear throughout the plant kingdom from the simple metabolites of lichens and fungi to the steroidal glycosides, and were even found in animal species such as sponges and insects. [3] This moiety confers a wide variety of biological properties such as cytotoxic, [4 -7] antifeeding, [8] phytotoxic and antibacterial, [9] antifungal, [10] insecticidal, [11] antiinflammatory, [12] and analgesic effects. [13] There are reports in the literature describing the potential use of compounds with this moiety as antitumor agents, [7,12] phospholipase A2 and cyclooxygenase inhibitors, [9] and antibiotics.…”

Section: Introductionmentioning

confidence: 99%

Furanose C—C‐linked γ‐lactones: a combined ESI FTICR MS and semi‐empirical calculations study

Madeira¹,

Xavier²,

Rauter³

et al. 2010

J. Mass Spectrom.

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Sugars that incorporate the unsaturated carbonyl motif have become important synthetic targets not only as a result of their potential biological properties but also as precursors in the synthesis of many bioactive products. Moreover, little is known about the influence of the γ-lactone moiety in the fragmentation pattern of furanose rings. Therefore, two α,β-unsaturated γ-lactones (butenolides) and two β-hydroxy γ-lactones, C-C linked to a furanose ring were studied using electrospray ionization FTICR mass spectrometry. The behaviour of the protonated and sodiated forms of the compounds under study has been compared considering their structural features. Fragmentation mechanisms were established and ion structures were proposed taking into account the MS(2) and MS(3) experiments, accurate mass measurements and semi-empirical calculations. These inexpensive methods proved to be a valuable resource for proposing protonation sites and for the establishment of fragmentation pathways.

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“…Selective tosylation of the primary hydroxyl group using tosyl chloride in presence of Bu 2 SnO and triethylamine furnished compound 8 in 75% yield [26,27]. Treatment of 8 with K 2 CO 3 in methanol gave the epoxide 9 in 90% yield [26,28] and then the oxirane 9 was reacted in presence of CuI in THF with pent-4-ene magnesium bromide to give selectively the (R) alcohol 10 in 89% yield. This condensation has occurred without any loss in the chiral integrity of the (R)-configuration at the C5 centre.…”

Section: Toward the Synthesis Of 3-n5′-c-cyclonucleosidesmentioning

confidence: 99%

Synthesis of a novel uridine analogue and its use in attempts to form new cyclonucleosides using ring-closing metathesis

2010

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Efficient synthesis of α,β-unsaturated γ-lactones linked to sugars

Cited by 51 publications

References 35 publications

Electrospray ionization mass spectrometric analysis of newly synthesized α,β‐unsaturated γ‐lactones fused to sugars

Electrospray ionization mass spectrometric analysis of newly synthesized α,β‐unsaturated γ‐lactones fused to sugars

Furanose C—C‐linked γ‐lactones: a combined ESI FTICR MS and semi‐empirical calculations study

Synthesis of a novel uridine analogue and its use in attempts to form new cyclonucleosides using ring-closing metathesis

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