Rhizochalin, a novel secondary metabolite of mixed biosynthesis from the sponge Rhizochalina incrustata

Makarieva, Tatiana N.; Денисенко, В. А.; Stonik, Valentin A.; Mil'grom, Yu. M.; Rashkes, Ya. V.

doi:10.1016/s0040-4039(01)89027-4

Cited by 69 publications

(105 citation statements)

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“…These molecules are mostly long chain amino alcohols and their potent biological activity which ranges from antimicrobial activity to inhibition of cell proliferation through prevention of the formation of actin stress fibers in cultured cells, [21][22][23][24][25][26][27][28][29] attracted many natural products chemists.…”

Section: Resultsmentioning

confidence: 99%

“…3,4 The structures of these molecules are generally related to the widely distributed amphiphilic sphingosine related long chain amino alcohols, [5][6][7] the central structural element of sphingolipids; their carbon chain varies from C 12 to C 30 and few of them have also polyunsaturated variants. [8][9][10][11][12] Their structures were established by thorough analysis of spectroscopic data and chemical conversion. These compounds showed cytotoxic and pro-apoptotic activities against different cell lines A549 (lung carcinoma), T47D (breast carcinoma) and AGS (gastric carcinoma), including cell death through activation of the apoptotic machinery.…”

Section: Introductionmentioning

confidence: 99%

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General synthetic strategy for clavaminols A, C and H

Thirupathi¹,

Bharath²,

Mohapatra³

2015

Arkivoc

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Dedicated to Dr. J. S. Yadav on the occasion of his 65th birthday and in appreciation of his outstanding contributions to synthetic organic chemistry DOI: http://dx.doi.org/10.3998/ark.5550190.p009.281 Abstract A general and efficient synthetic strategy has been developed for the total syntheses of clavaminols A, C and H in 5 to 7 steps starting from (R)-Garners aldehyde following Grignard reaction, Corey-Bakshi-Shibata asymmetric reduction and selective acetylation as key steps with 42 to 59% overall yields, respectively.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

General synthetic strategy for clavaminols A, C and H

Thirupathi¹,

Bharath²,

Mohapatra³

2015

Arkivoc

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“…Mitochondrial Permeability Assay Rhz-treated HL-60 cells (1ϫ10 6 /ml) were exposed to 40 nM of 3,30-dihexyloxacarbocyanine iodide [DiOC 6 (3), Molecular probes] for 30 min at 37°C and then washed with PBS. Stained cells were analyzed by flow cytometry.…”

Section: Purification Of Rhz or Its Analogs And Preparation Of Its Dementioning

confidence: 99%

“…1), isolated in 1989 by our group from the Madagascarian sponge Rhizochalin incrustata. 6) The group of two-headed sphingolipids includes a limited number of compounds: Rhz, Rhz A, Rhz C, Rhz D and rhizochalinin A from the marine sponge Rhizochalina incrustata, [6][7][8][9][10] oceanapiside from Oceanapia phillipensis, 11) oceanalin A, Rhz B, and rhizochalinin B from Oceanapia sp., 7,12) calyxoside from Calyx sp., 13) leucettamols A and B from Leucetta leptorhapsis 14) and compound BRS1 from an unidentified sponge. 15) Their structures have been established on the basis of spectroscopic data and chemical transformations.…”

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confidence: 99%

“…Previous investigation of the biological properties of two-headed sphingolipids revealed antibacterial activity of Rhz against Staphylococcus aureus and cytotoxic activity against mouse Ehrlich carcinoma cells (IC 50 , 10 mg/ ml). 6) Another analogue of Rhz, calyxoside is a selective DNA-damaging agent, but lacks inhibitory activity against topoisomerase I or II. 13) Oceanalin A and oceanapiside exhibit significant antifungal activity against the pathogenic…”

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Differential Induction of Apoptosis of Leukemic Cells by Rhizochalin, Two Headed Sphingolipids from Sponge and Its Derivatives

Jin

Shastina

Park

et al. 2009

Biological & Pharmaceutical Bulletin

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(−)-Rhizochalin is a Dimeric Enantiomorphic (2R)-Sphingolipid: Absolute Configuration of Pseudo-C2v-Symmetric Bis-2-amino-3-alkanols by CD

2000

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Sphingolipids are well-known cellular components of all higher eukaryotes and have attracted renewed interest with the finding that erythro-d-sphingosine (1 a) and its derivatives, such as ceramides (N-fatty acyl sphingosines) and sphinosine 1-O-phosphate, have important roles in higher mammals as ªfirst messengersº. [1] Highly modified sphingolipids, such as the sphingofungins, [2] occur in lower invertebrates and microbes and may also function as inhibitors of various pathways in mammalian sphingolipid biosynthesis. (À)-Rhizochalin (2), an antimicrobial galactopyranosyl pseudodimeric a,w-bipolar sphingolipid, was isolated from the calcareous sponge Rhizochalina incrustata, [3] collected near Madagascar. Although the constitutional structure of 2 was established from spectroscopic and degradative analysis, the stereostructure remained undefined.Configurational analysis of sphingosine diasteromers by circular dichroism (CD) has been reported. [4,5] We have previously devised a CD method for a,w-bis-sphingoid bases that exploits deconvolution of superposed exciton couplings in the CD spectrum of the corresponding tetrabenzoyl derivatives [6] and we applied this to the antifungal agent oceanapiside (3), [7] a related a,w-sphingolipid isolated from a temperate-water marine sponge, Oceanapia phillipensis Dendy 1895 (Haplosclerida, Phloeodictyidae). The technique is noteworthy for simplicity, particularly with respect to dimeric amino alkanols, ample sensitivity (% 50 nmol), and complementarity with other CD methods for the configurational analysis of sphingolipids. [4,5,8] Whereas the chain termini in 3 have dissimilar substitution, the pseudosymmetric structure of 2 presents the added challenge of correlating remote end groups in pseudo-C 2vsymmetric or meso dimeric stereoisomers of a,w-difunctionalized long chains. Identification of meso compounds is trivial (lack of optical activity), but the former stereoisomers present a problem that is refractory to simple end-group analysis by NMR spectroscopy or measurement of optical rotation because the methods do not correlate the chain termini or they lack sensitivity. We show now, by the exciton-coupling CD superposition method, that the complete configuration of (À)-rhizochalin (2) is 2R,3R,26R,27R and we note a remarkable findingÐboth ends of 2 are threo and enantiomeric to those of known 2-amino-3-alkanol sphingolipids. This suggests that stepwise biosynthesis of bipolar sphingolipids in marine sponges is a highly ordered process that may selfregulate cognate precursor selection for chain assembly.A suitable chromophoric derivative of 2 was prepared as follows (Scheme 1). The aglycone, 4, obtained by methanolysis of 2 (MeOH, 1m HCl, 75 8C, 24 h), was transformed into the corresponding tetrabenzoyl derivative 5 (N-benzoylimidazole, CH 3 CN, catalytic DBU, 70 8C, 24 h), [9] which was subsequently purified by HPLC (% 50 nmol). Benzoylation of 4 with BzCl/pyridine (60 or 100 8C) was less suitable and resulted in extensive formation of the bis-oxazoline 6.The CD spectra of...

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Rhizochalin, a novel secondary metabolite of mixed biosynthesis from the sponge Rhizochalina incrustata

Cited by 69 publications

References 1 publication

General synthetic strategy for clavaminols A, C and H

General synthetic strategy for clavaminols A, C and H

Differential Induction of Apoptosis of Leukemic Cells by Rhizochalin, Two Headed Sphingolipids from Sponge and Its Derivatives

(−)-Rhizochalin is a Dimeric Enantiomorphic (2R)-Sphingolipid: Absolute Configuration of Pseudo-C2v-Symmetric Bis-2-amino-3-alkanols by CD

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