Novel methoxylated FA from the Caribbean sponge <i>Spheciospongia cuspidifera</i>

Carballeira, Néstor M.; Alicea, Johanna

doi:10.1007/s11745-002-0895-1

“…Among the studied FA from P. suberitoides a novel amethoxylated fatty acid, namely 4, was also characterized using GC-MS as well as gas chromatographic ECL values as compared to synthetic standards [14,19]. The mass spectrum of the methyl ester of 4 displayed a molecular ion peak at m/z 286 and a strong M + -59 peak at m/z 227 (100%), together with a small peak at m/z 104 (McLafferty rearrangement), all typical mass fragments for a-methoxylated saturated methyl esters [14,19].…”

Section: Resultsmentioning

confidence: 99%

“…The mass spectrum of the methyl ester of 4 displayed a molecular ion peak at m/z 286 and a strong M + -59 peak at m/z 227 (100%), together with a small peak at m/z 104 (McLafferty rearrangement), all typical mass fragments for a-methoxylated saturated methyl esters [14,19]. The a-methoxylation was further confirmed by 1 H NMR spectroscopy since it was also possible to observe the characteristic signals of the a-methoxy methyl ester in the 1 H NMR spectrum of the whole FAME mixture without interference from other peaks.…”

Section: Resultsmentioning

confidence: 99%

Novel Cyclopropane Fatty Acids from the Phospholipids of the Caribbean Sponge Pseudospongosorites suberitoides

Carballeira

¹

,

Montano

²

,

Vicente

³

et al. 2007

Lipids

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The cyclopropane fatty acids 17-methyl-trans-4,5-methyleneoctadecanoic acid, 18-methyl-trans-4,5-methylenenonadecanoic acid, and 17-methyl-trans-4,5-methylenenonadecanoic acid were characterized for the first time in nature in the phospholipids (mainly PE, PG and PS) of the hermit-crab sponge Pseudospongosorites suberitoides. Pyrrolidine derivatization was the key in identifying the position of the cyclopropyl and methyl groups in the acyl chains and (1)H NMR was used to determine the trans stereochemistry of the cyclopropane ring. The phospholipids from the sponge also contained an interesting series of iso-anteiso Delta(5,9) fatty acids with chain-lengths between 17 and 21 carbons, with the fatty acids (5Z,9Z)-18-methyl-5,9-nonadecadienoic acid and the (5Z,9Z)-17-methyl-5,9-nonadecadienoic acid being described for the first time in sponges. The anteiso alpha-methoxylated fatty acid 2-methoxy-12-methyltetradecanoic acid was also identified for the first time in nature in the phospholipids of this interesting marine sponge. The novel cyclopropyl fatty acids could have originated from the phospholipids of a cyanobacterium living in symbiosis with the sponge.

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“…The final acid 2 was obtained after methylation of 13 with sodium hydride and methyl iodide in THF, following an acidic workup, resulting in the (6 Z )-(±)-2-methoxy-6-octadecenoic acid ( 2 ) in a 90 % yield. The overall yield for this eight-step synthetic sequence (starting from 5 ) was 13 %, and this is the first reported total synthesis for 2 [12]. …”

Section: Resultsmentioning

confidence: 99%

“…Was synthesized from the catalytic hydrogenation of 3 in hexane with H 2 and 10% Pd/C and the purity of the final product was confirmed by 13 C-NMR spectroscopy as well as comparison of the MS spectral data with the one previously reported [12]. …”

Section: Methodsmentioning

confidence: 99%

“…Compounds 1 and 2 are ideal to be compared to the corresponding non methoxylated analogs since it has been well established in the literature that 16:1 isomers, in particular the 6- and 9-hexadecenoic acids, are toxic towards S. aureus while the 18:1 isomers, such as the 6- and 9-octadecenoic acids, are relatively nontoxic to some S. aureus strains [11]. In this work we also present the first total synthesis for 2 , a natural product previously identified by us in the Caribbean sponge Spheciospongia cuspidifera [12] as well as a third generation synthesis for 1 , initially isolated from the same sponge.…”

Section: Introductionmentioning

confidence: 97%

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2‐Methoxylated FA Display Unusual Antibacterial Activity Towards Clinical Isolates of Methicillin‐Resistant Staphylococcus aureus (CIMRSA) and Escherichia coli

Carballeira

¹

,

Montano

²

,

Morales

³

et al. 2017

Lipids

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The naturally occurring (6Z)-(±)-2-methoxy-6-hexadecenoic acid (1) and (6Z)-(±)-2-methoxy-6-octadecenoic acid (2) were synthesized in 7–8 steps with 38% and 13% overall yields, respectively, by using an acetylide coupling approach, which made it possible to obtain a 100% cis-stereochemistry for the double bonds. In a similar fashion, the acetylenic analogs (±)-2-methoxy-6-hexadecynoic acid (3) and (±)-2-methoxy-6-octadecynoic acid (4) were also synthesized in 6–7 steps with 48% and 16% overall yields, respectively. The antibacterial activity of acids 1–4 was determined against clinical isolates of methicillin-resistant Staphylococcus aureus (ClMRSA) and E. coli. Among the series of compounds, acid 4 was the most active bactericide towards CIMRSA displaying IC50s (half maximal inhibitory concentrations) between 17–37 µg/mL, in sharp contrast to the 6-octadecynoic acid, which was not bactericidal at all. On the other hand, acids 1 and 3 were the only acids that displayed antibacterial activity towards E. coli, but 1 stood out as the best candidate with an IC50 of 21 µg/mL. The critical micelle concentrations (CMCs) of acids 1–4 were also determined. The C18 acids 2 and 4 displayed a five-fold lower CMC (15–20 µg/mL) than the C16 analogs 1 and 3 (70–100 µg/mL), indicating that 4 exerts its antibacterial activity in a micellar state. None of the studied acids were inhibitory towards S. aureus DNA gyrase discarding this type of enzyme inhibition as a possible antibacterial mechanism. It was concluded that the combination of α-methoxylation and C-6 unsaturation increases the bactericidal activity of the C16 and C18 FA towards the studied bacterial strains. Acids 1 and 4 stand out as viable candidates to be used against E. coli and CIMRSA, respectively.

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Porifera (Sponges)–1

Kornprobst

¹

2014

Encyclopedia of Marine Natural Products

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The article contains sections titled: Overview of the Universe of Sponges Metabolites of Calcarea (Calcareous Sponges) General Characteristics of Calcarea Fatty Acids Sterols Non‐Nitrogenous Derivatives of Species of the Genus Leucetta Imidazole Alkaloids and Zinc Complexes Isolated from the Genera Leucetta , Leucosolenia , and Clathrina αω‐ Bis Long‐Chain Aminoalcohols Nitrogen‐Containing Macrolides and Cyclic Peptides Other Nitrogen‐Containing Compounds of Calcarea Metabolites of Hexactinellida Classification and Membrane Constituents of Demospongiae Classification Some Physical Observations on Demosponges Shape and Size Consistency Color and Odor Diversity of Membrane Constituents: Some Examples Phospholipids and “Demospongic Acids” Fatty Acids with 5,9 Dienic Structure Other Mono‐ and Polyunsaturated Fatty Acids Branched Fatty Acids Isoprenic Acids Cyclopropanic Acids Brominated Acids 2‐ O Substituted Acids Sulfur Derivatives of Demospongic Acids Intracellular Localization and Biological Activity of Demospongic Acids Brief Reminder About Conventional Sterols Unconventional Sterols Produced by Changes in the Tetracyclic System Unconventional Sterols Produced by Polymethylation of the Side Chain Sterols with Degraded Side Chains Sterols and Stanols with Cyclopropanic and Cyclopropenic Side Chains Secosterols Polyhydroxylated Steroids and Derivatives, Peroxysterols Sulfated Sterols Chlorinated Sterols and Sterones Nitrogen‐Containing Sterols Glycolipids Secondary Metabolites of Homoscleromorpha Fatty Acids, Polyketides and Oxylipins of Plakinastrella and Plakortis Cyclic Peroxides and Peroxylactones from Plakinastrella and Plakortis Glycosides Polyhydroxylated Sterols of Oscarella lobularis Alkaloids and Other Original Nitrogen Derivatives of Plakortis and Corticium Secondary Metabolites of Astrophorida Acetylenic Fatty Acids of Stelletta Cyclitol Derivatives Glycolipids: Caminosides and Pachymosides Triterpenes of Malabaricane and Isomalabaricane: Sesterterpenes Triterpenic Glycosides and Steroidal Glycosides Substituted Tetramic Acids and Derived Glycosides Erylusamines, Erylusine, and Erylusidine Cyclic Depsipeptides, Peptolides, and Macrolactones Nitrogen‐Containing Terpenes Bengazoles and Bengamides Atypical Nitrogenous Derivatives Phosphorus‐Containing Derivatives Aromatic and Heteroaromatic Sulfated Derivatives Isotactic Polymethoxydienes of Myriastra clavosa

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Novel methoxylated FA from the Caribbean sponge Spheciospongia cuspidifera

Cited by 12 publications

References 12 publications

Novel Cyclopropane Fatty Acids from the Phospholipids of the Caribbean Sponge Pseudospongosorites suberitoides

Novel Cyclopropane Fatty Acids from the Phospholipids of the Caribbean Sponge Pseudospongosorites suberitoides

2‐Methoxylated FA Display Unusual Antibacterial Activity Towards Clinical Isolates of Methicillin‐Resistant Staphylococcus aureus (CIMRSA) and Escherichia coli

Porifera (Sponges)–1

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