cas 123-78-4, D-ERYTHRO-SPHINGOSINE | Articles data

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An efficient synthesis of D-erythro- and D-threo-sphingosine from D-glucose: Olefin cross-metathesis approach
(Chemical Equation Presented) The D-erythro- and D-threo-sphingosine were synthesized via E-selective olefin cross-metathesis using a D-glucose-derived building block and long-chain terminal alkene.
Chaudhari, Vinod D.,Ajish Kumar,Dhavale, Dilip D.
p. 5805 - 5807
(2005)
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Aziridine-2-carboxylic acid mediated asymmetric synthesis of D-erythro-and L-threo-sphingosine from a common precursor
Short, two and three step asymmetric syntheses of L-threo- and D-erythrosphingosine (-)-6a and (-)-9a, respectively, in 58 and 31 percent overall yield were accomplished via the stereo and regioselective ring opening of N-sulfinylaziridine 2-carboxylic acid 4. Copyright
Davis, Franklin A.,Reddy, G. Venkat
p. 4349 - 4352
(1996)
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Highly Diastereoselective Synthesis of D-threo- and D-erythro-Sphingosine from Glycidol
D-Threo- and D-erythro-sphingosine, (1) and (2), inhibitors of protein kinase C, have been efficiently synthesized from glycidol through (R)-4-methoxycarbonyloxazolidinone (3) by selective mono-alkylation followed by highly diastereoselective reduction of the tin-substituted pentadecenyl ketone 5.
Katsumura, Shigeo,Yamamoto, Noriyoshi,Fukuda, Etsuko,Iwama, Seiji
p. 393 - 394
(1995)
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A stereoselective synthesis of d-erythro-spingosine.
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Newman
p. 4098 - 4099
(1973)
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Amplification of a FRET Probe by Lipid–Water Partition for the Detection of Acid Sphingomyelinase in Live Cells
Real-time monitoring of acid sphingomyelinase (ASM) activity is crucial for investigating its role in lipid-mediated signaling processes. In this study, we synthesized fluorescent phosphosphingolipids capable of FRET by phosphorodichloridate chemistry. These sphingomyelin analogues are substrates for recombinant human ASM and can be used to monitor ASM activity by fluorescence spectroscopy. Incubation with cell lysates from wild-type and knock-out mice further confirmed probe cleavage to be exclusive to ASM. We also systematically exploited the environmental sensitivity of the fluorophores to achieve significant increases in responsiveness. This concept may be transferred to other lipid probes in the future. The ASM activity in live cells was imaged by two-photon-excitation microscopy.
Pinkert, Thomas,Furkert, David,Korte, Thomas,Herrmann, Andreas,Arenz, Christoph
p. 2790 - 2794
(2017)
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Calyceramides A-C: Neuraminidase inhibitory sulfated ceramides from the marine sponge Discodermia calyx
Three new sulfated ceramides, calyceramides A-C (1-3) were isolated as inhibitors of neuraminidase from the marine sponge Discodermia calyx. Their structures were determined by spectroscopic and chemical methods. The ceramides inhibited neuraminidase with IC50 values of 0.2-0.8 μg mL-1.
Nakao, Yoichi,Takada, Kentaro,Matsunaga, Shigeki,Fusetani, Nobuhiro
p. 3013 - 3017
(2001)
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N-Metallocenoylsphingosines as targeted ceramidase inhibitors: Syntheses and antitumoral effects
Three N-metallocenoylsphingosines with variance in the central metal (Fe, Co, Ru), the charge (neutral or cationic), and the arene ligands (Cp2, Cp*Ph) were synthesized from serine and metallocene carboxylic acids as substrate-analogous inhibit
Klatt, Felix,Kuhn, Claus-D.,Rothemund, Matthias,Schobert, Rainer,Unverzagt, Carlo,Weidler, Sascha,B?r, Alexander,K?hler, Leonhard
(2020)
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Synthesis of trans- and cis-sphingosine.
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Reist,Christie
p. 4127 - 4130
(1970)
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Divergent synthesis of diastereomeric sphingosines from a chiral aziridine
All four stereoisomers of sphingosines were synthesized starting from a single intermediate, chiral aziridine (2), which was efficiently prepared by enzymatic desymmetrization in an enatiopure form. Aziridine (2) was converted to 3, which was used for the synthesis of 4. Both the advanced key intermediates, vinylaziridines 3 and 4, were successfully converted to threo-sphingosines 1a and 1b, respectively. Ring-closing metathesis (RCM) using the Grubbs II catalyst was the key reaction in the synthesis. Two erythro-sphingosines 1c and 1d were synthesized by the ring-expansion reactions of vinylaziridines 3 and 4, followed by RCM reactions. The successful divergent synthesis confirmed that chiral vinylaziridine 2 can be used as a key intermediate for the synthesis of sphingosine-related natural products.
Kang, On-Yu,Shin, Mi-Ri,Kang, Han-Young
p. 1095 - 1104
(2016)
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Synthesis and evaluation of novel phosphate ester analogs as neutral sphingomyelinase inhibitors
A novel sphingomyelin inhibitor RY221B-a, which contains a bipyridyl moiety as a metal coordination site was designed based upon the mechanism of phosphate ester hydrolysis. RY221B-a was synthesized from N-Boc-sphingosine in three steps via selective etherification using stannyl acetal. Synthesized RY221B-a exhibited relatively-strong inhibitory activity against Bc-SMase (IC 50 = 1.2 μM).
Imagawa, Hiroshi,Oda, Masataka,Takemoto, Takayuki,Yamauchi, Rieko,Yoshikawa, Tomomi,Yamamoto, Hirofumi,Nishizawa, Mugio,Takahashi, Hironobu,Hashimoto, Manabu,Yabiku, Kenta,Nagahama, Masahiro,Sakurai, Jun
p. 3868 - 3871
(2010)
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A short enantiodivergent synthesis of D-erythro and L-threo sphingosine
A new, short (6 steps) and efficient enantiodivergent route to both D-erythro and L threo-sphingosine I and II is disclosed. The high diastereoselection (100% de) reached in the creation of the C-3 stereocenter relies on the use of a sulfoxide as chiral controlling agent in the reduction of the common precursor β-keto sulfoxide 3. The desired E-alkene of sphingosines has been constructed by the Schlosser modification of the Wittig reaction between the aldehyde 8 and the phosphonium salt 9. The reported methodology can easily be extended to the synthesis of a large number of optically pure syn and anti amino alcohols starting from commercially available amino acids.
Khiar, Noureddine,Singh, Kamaljit,Garcia, Mercedes,Martin-Lomas, Manuel
p. 5779 - 5782
(1999)
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ASYMMETRIC SYNTHESIS OF THREO- AND ERYTHRO-SPHINGOSINES BY ASYMMETRIC ALDOL REACTION OF α-ISOCYANOACETATE CATALYZED BY A CHIRAL FERROCENYLPHOSPHINE-GOLD(I) COMPLEX
Asymmetric aldol reaction of methyl α-isocyanoacetate with (E)-2-hexadecenal in the presence of 1 molpercent of a chiral (aminoalkyl)ferrocenylphosphine-gold(I) complex gave optically active trans -4-(methoxycarbonyl)-5--2-oxazoline (93percent ee) which was readily converted into D-threo- and erythro -sphingosines
Ito, Yoshihiko,Sawamura, Masaya,Hayashi, Tamio
p. 239 - 240
(1988)
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New cytotoxic cerebrosides from the red sea cucumber Holothuria spinifera supported by in-silico studies
Bioactivity-guided fractionation of a methanolic extract of the Red Sea cucumber Holothuria spinifera and LC-HRESIMS-assisted dereplication resulted in the isolation of four compounds, three new cerebrosides, spiniferosides A (1), B (2), and C (3), and cholesterol sulfate (4). The chemical structures of the isolated compounds were established on the basis of their 1D NMR and HRMS spectral data. Metabolic profiling of the H. spinifera extract indicated the presence of diverse secondary metabolites, mostly hydroxy fatty acids, diterpenes, triterpenes, and cerebrosides. The isolated compounds were tested for their in vitro cytotoxicities against the breast adenocarcinoma MCF-7 cell line. Compounds 1, 2, 3, and 4 displayed promising cytotoxic activities against MCF-7 cells, with IC50 values of 13.83, 8.13, 8.27, and 35.56 μM, respectively, compared to that of the standard drug doxorubicin (IC50 8.64 μM). Additionally, docking studies were performed for compounds 1, 2, 3, and 4 to elucidate their binding interactions with the active site of the SET protein, an inhibitor of protein phosphatase 2A (PP2A), which could explain their cytotoxic activity. This study highlights the important role of these metabolites in the defense mechanism of the sea cucumber against fouling organisms and the potential uses of these active molecules in the design of new anticancer agents.
Abdelhameed, Reda F.A.,Eltamany, Enas E.,Hal, Dina M.,Ibrahim, Amany K.,AboulMagd, Asmaa M.,Al-Warhi, Tarfah,Youssif, Khayrya A.,Abd El-Kader, Adel M.,Hassanean, Hashim A.,Fayez, Shaimaa,Bringmann, Gerhard,Ahmed, Safwat A.,Abdelmohsen, Usama Ramadan
(2020/09/07)

Liposomal FRET Assay Identifies Potent Drug-Like Inhibitors of the Ceramide Transport Protein (CERT)
Ceramide transfer protein (CERT) mediates non-vesicular transfer of ceramide from endoplasmic reticulum to Golgi apparatus and thus catalyzes the rate-limiting step of sphingomyelin biosynthesis. Usually, CERT ligands are evaluated in tedious binding assays or non-homogenous transfer assays using radiolabeled ceramides. Herein, a facile and sensitive assay for CERT, based on F?rster resonance energy transfer (FRET), is presented. To this end, we mixed donor and acceptor vesicles, each containing a different fluorescent ceramide species. By CERT-mediated transfer of fluorescent ceramide, a FRET system was established, which allows readout in 96-well plate format, despite the high hydrophobicity of the components. Screening of a 2 000 compound library resulted in two new potent CERT inhibitors. One is approved for use in humans and one is approved for use in animals. Evaluation of cellular activity by quantitative mass spectrometry and confocal microscopy showed inhibition of ceramide trafficking and sphingomyelin biosynthesis.
Aglar, ?znur,Arenz, Christoph,Banhart, Sebastian,Cong, Xiaojing,Hamdo, Housam H.,Heuer, Dagmar,Kleuser, Burkhard,M?ller, Heiko M.,Saied, Essa M.,Samaha, Doaa,Schumacher, Fabian
supporting information
p. 16616 - 16621
(2020/11/30)

Synthesis of Gb3 Glycosphingolipids with Labeled Head Groups: Distribution in Phase-Separated Giant Unilamellar Vesicles
The receptor lipid Gb3 is responsible for the specific internalization of Shiga toxin (STx) into cells. The head group of Gb3 defines the specificity of STx binding, and the backbone with different fatty acids is expected to influence its localization within membranes impacting membrane organization and protein internalization. To investigate this influence, a set of Gb3 glycosphingolipids labeled with a BODIPY fluorophore attached to the head group was synthesized. C24 fatty acids, saturated, unsaturated, α-hydroxylated derivatives, and a combination thereof, were attached to the sphingosine backbone. The synthetic Gb3 glycosphingolipids were reconstituted into coexisting liquid-ordered (lo)/liquid-disordered (ld) giant unilamellar vesicles (GUVs), and STx binding was verified by fluorescence microscopy. Gb3 with the C24:0 fatty acid partitioned mostly in the lo phase, while the unsaturated C24:1 fatty acid distributes more into the ld phase. The α-hydroxylation does not influence its partitioning.
Sibold, Jeremias,Kettelhoit, Katharina,Vuong, Loan,Liu, Fangyuan,Werz, Daniel B.,Steinem, Claudia
supporting information
p. 17805 - 17813
(2019/11/13)

SPHINGOSINE/SPHINGOID BASE PRODUCTION
The present invention relates to sphingolipids, and more particularly to a method for the production of sphingoid bases, especially sphingosine, and novel derivatives thereof. The sphingoid bases are herein produced by making use of a vinylogous amide-type protecting group. The resulting vinylogous amide compounds enable an easy and effective production of sphingoid bases, especially sphingosine.
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Page/Page column 35-36

(2020/01/08)

Lipidated cyclopropenes via a stable 3-N spirocyclopropene scaffold
Lipidated cyclopropenes serve as useful bioorthogonal reagents for imaging cell membranes due to the cyclopropene's small size and ability to ligate with pro-fluorescent tetrazines. Previously, the lipidation of cyclopropenes required modification at the C3 position because methods to append lipids at C1/C2 were not available. Herein, we describe C1/C2 lipidation with the biologically active lipid ceramide and a common phospholipid using a cyclopropene scaffold whose reactivity with 1,2,4,5-tetrazines has been caged.
Kumar, Pratik,Jiang, Ting,Zainul, Omar,Preston, Alyssa N.,Li, Sining,Farr, Joshua D.,Suri, Pavit,Laughlin, Scott T.
supporting information
p. 3435 - 3438
(2018/08/21)

A rapid synthesis of sphingosine from phytosphingosine
A simple and efficient protocol for the synthesis of a sphingosine starting from cost-effective phytosphingosine has been described. Two alternative synthetic pathway have been disclosed based on the use of two different kinds of protective groups for the protection of the amino group in the phytosphingosine. The protected phytosphingosine was subsequently transformed into sphingosine in 5 steps i.e. protection of the amine group, protection of 1,3-diol, leaving group insertion, elimination, and one-pot deprotection.
Sankar, Arumugam,Chen, I-Cheng,Luo, Shun-Yuan
p. 1 - 5
(2018/05/03)

D-erythro-sphingosine synthesis method
The invention relates to a D-erythro-sphingosine synthesis method, comprising the steps of dissolving a compound 6 into dry tetrahydrofuran, adding lithium aluminum hydride under protection of nitrogen, after complete reaction of a raw material, adding a potassium sodium tartrate solution and finishing; extracting through ethyl acetate, concentrating and performing column chromatography; separating to obtain D-erythro-sphingosine. Compared with a traditional method, the synthesis method provided by the invention has the advantages that the use of a large amount of strong base phenyl lithium in a Wittig reaction process is avoided, meanwhile, the yield is increased; an azidation reaction adopts a two-step method of iodination and then azidation, and low temperature reaction in the existing technical scheme is not needed, so that the operation is more convenient and simple.
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Paragraph 0021; 0022; 0038; 0039

(2017/08/31)

Modular Construction of Protected 1,2/1,3-Diols, -Amino Alcohols, and -Diamines via Catalytic Asymmetric Dehydrative Allylation: An Application to Synthesis of Sphingosine
A new enantioselective catalysis has been developed for the one-step construction of methylene-bridged chiral modules of 1,2- and 1,3-OH and/or NH function(s) from δ- or λ-OH/NHBoc-substituted allylic alcohols and H2C=O / H2C=NBoc . A protonic nucleophile, either in situ-generated CH2OH or CH2NHBoc, is intramolecularly allylated to furnish eight possible 1,2- or 1,3-O,O, -O,N, -N,O, and -N,N chiral modules equipped with an ethenyl group in high yields and enantioselectivities. The utility of this method has been demonstrated in the five-step synthesis of sphingosine.
Tanaka, Shinji,Gunasekar, Ramachandran,Tanaka, Tatsuya,Iyoda, Yoko,Suzuki, Yusuke,Kitamura, Masato
p. 9160 - 9170
(2017/09/11)

NOVEL SYNTHESIS INTERMEDIATES FOR OBTAINING DERIVATIVES OF SPHINGOSINES, CERAMIDES AND SPHINGOMYELINS WITH GOOD YIELDS
The subject matter of the present invention is the novel molecules of formulae E, E′ and F. These molecules prove to be synthesis intermediates that are very advantageous for the manufacture of derivatives of sphingosine or of ceramides functionalized in position 1, with good yields, in which R1 and R2 are fatty chains, R3 is an alkyl group and R4 is a protective group for alcohol functions. Another subject of the invention is the use of the intermediates of type F for converting same into intermediates of type G, by means of reduction in the presence of lithium borohydride. The G molecules are precursors that are known to make it possible to obtain sphingolipids or sphingomyelin.
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Paragraph 0086; 0087; 0088; 0089; 0090

(2016/04/19)

METHODS FOR THE SYNTHESIS OF SPHINGOMYELINS AND DIHYDROSPHINGOMYELINS
The present invention includes methods for the synthesis of sphingomyelins and dihydrosphingomyelins. The present invention also includes methods for the synthesis of sphingosines and dihydrosphingosines. The present invention further includes methods for the synthesis of ceramides and dihydroceramides.
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Paragraph 0315-0317

(2014/09/30)

METHODS FOR THE SYNTHESIS OF SPHINGOMYELINS AND DIHYDROSPHINGOMYELINS
The present invention includes methods for the synthesis of sphingomyelins and dihydrosphingomyelins. The present invention also includes methods for the synthesis of sphingosines and dihydrosphingosines. The present invention further includes methods for the synthesis of ceramides and dihydroceramides.
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Paragraph 00262; 00263

(2014/09/29)

Rhodium-catalyzed regio- and stereoselective oxyamination of dienes via tandem aziridination/ring-opening of dienyl carbamates
The reaction of dienyl carbamates with PhI(OR)2 in the presence of rhodium catalysts affords vinyl aziridines which are in situ regio- and stereoselectively opened to afford oxyamination products resulting from a selective SN2 (Rh2(OAc)4/PhI(OPiv)2) or SN2′ (Rh2(OPiv)4/PhI(OAc) 2) opening. The scope and limitations of this tandem process are described.
Guasch, Joan,Díaz, Yolanda,Matheu, M. Isabel,Castillón, Sergio
supporting information
p. 7344 - 7347
(2014/07/07)

Chemo-, regio-, and stereoselective silver-catalyzed aziridination of dienes: Scope, mechanistic studies, and ring-opening reactions
Silver complexes bearing trispyrazolylborate ligands (Tpx) catalyze the aziridination of 2,4-diene-1-ols in a chemo-, regio-, and stereoselective manner to give vinylaziridines in high yields by means of the metal-mediated transfer of NTs (Ts = p-toluensulfonyl) units from PhI=NTs. The preferential aziridination occurs at the double bond neighboring to the hydroxyl end in ca. 9:1 ratios that assessed a very high degree of regioselectivity. The reaction with the silver-based catalysts proceeds in a stereospecific manner, i.e., the initial configuration of the C=C bond is maintained in the aziridine product (cis or trans). The degree of regioselectivity was explained with the aid of DFT studies, where the directing effect of the OH group of 2,4-diene-1-ols plays a key role. Effective strategies for ring-opening of the new aziridines, deprotection of the Ts group, and subsequent formation of β-amino alcohols have also been developed.
Llaveria, Josep,Beltrán, álvaro,Sameera,Locati, Abel,Díaz-Requejo, M. Mar,Matheu, M. Isabel,Castillón, Sergio,Maseras, Feliu,Pérez, Pedro J.
p. 5342 - 5350
(2014/05/06)

Neritinaceramides A-E, new ceramides from the marine bryozoan Bugula neritina inhabiting South China Sea and their cytotoxicity
Five new ceramides, neritinaceramides A (1), B (2), C (3), D (4) and E (5), together with six known ceramides (6-11), two known alkyl glycerylethers (12 and 13) and a known nucleoside (14), were isolated from marine bryozoan Bugula neritina, which inhabits the South China Sea. The structures of the new compounds were elucidated as (2S,3R,3′S,4E,8E,10E)-2-(hexadecanoylamino)- 4,8,10-octadecatriene-l,3,3′-triol (1), (2S,3R,2′R,4E,8E,10E)-2- (hexadecanoylamino)-4,8,10-octadecatriene-l,3,2′-triol (2), (2S,3R,2′R,4E,8E,10E)-2-(octadecanoylamino)-4,8,10-octadecatriene-l,3, 2′-triol (3), (2S,3R,3′S,4E,8E)-2-(hexadecanoylamino)-4,8- octadecadiene-l,3,3′-triol (4) and (2S,3R,3′S,4E)-2- (hexadecanoylamino)-4-octadecene-l,3,3′-triol (5) on the basis of extensive spectral analysis and chemical evidences. The characteristic C-3′S hydroxyl group in the fatty acid moiety in compounds 1, 4 and 5, was a novel structural feature of ceramides. The rare 4E,8E,10E-triene structure in the sphingoid base of compounds 1-3, was found from marine bryozoans for the first time. The new ceramides 1-5 were evaluated for their cytotoxicity against HepG2, NCI-H460 and SGC7901 tumor cell lines, and all of them exhibited selective cytotoxicity against HepG2 and SGC7901 cells with a range of IC 50 values from 47.3 μM to 58.1 μM. These chemical and cytotoxic studies on the new neritinaceramides A-E (1-5) added to the chemical diversity of B. neritina and expanded our knowledge of the chemical modifications and biological activity of ceramides.
Tian, Xiang-Rong,Tang, Hai-Feng,Feng, Jun-Tao,Li, Yu-Shan,Lin, Hou-Wen,Fan, Xiao-Pei,Zhang, Xing
p. 1987 - 2003
(2014/06/09)

Facile and efficient addition of terminal alkynes to benzotriazole esters: Synthesis of d-erythro-sphingosine using ynones as the key intermediate
From the perspective of synthesis, ynones are compounds of considerable interest because of their occurrence in a wide variety of biologically active molecules and as key synthetic intermediates. In this context, a facile and highly efficient synthesis of ynones was developed based on the high reactivity of benzotriazole esters formed in situ. Lithium acetylides can alkylate various carboxylic acids in yields ranging from 60% to 92%. To determine whether our methodology is useful for synthesising complex and biologically relevant molecules, we synthesise d-erythro-sphingosine in four steps and with 33% overall yield from l-serine.
Morales-Serna, José Antonio,Sauza, Alejandro,Padrón De Jesús, Gabriela,Gavi?o, Rubén,García De La Mora, Gustavo,Cárdenas, Jorge
supporting information
p. 7111 - 7114
(2013/12/04)

Enantio- and diastereoselective syntheses of 3-hydroxypiperidines through iridium-catalyzed allylic substitution
Stereoselective syntheses of 3-hydroxypiperidines have been developed. Key intermediates are N-protected allylamines that are prepared by an enantioselective iridium-catalyzed allylic amination. A subsequent catch and release procedure that involves an epoxidation and base-mediated elimination yields δ-lactams that are suitably functionalized to prepare biologically active 3-hydroxypiperidines. In addition, applications of this method to the total syntheses of deoxymannojirimycin, D-erythro-sphingosine, and chiral building blocks of interest for medicinal chemistry are described. Stereoselective syntheses of 3-hydroxypiperidines are reported. The key reactions are an iridium-catalyzed allylic amination and a catch and release procedure that consists of a highly diastereoselective epoxidation and a base-mediated ring opening of the epoxide. This method was applied to the total syntheses of sphingosine, deoxymannojirimycin, and pharmaceutically relevant small molecules. Copyright
Hoecker, Johannes,Rudolf, Georg C.,Baechle, Florian,Fleischer, Steffen,Lindner, Benjamin D.,Helmchen, Guenter
supporting information
p. 5149 - 5159
(2013/11/06)

A highly stereoselective synthesis of glycidic amides based on a new class of chiral sulfonium salts: Applications in asymmetric synthesis
A new type of chiral sulfonium salts that are characterized by a bicyclic system has been designed and synthesized from α-amino acids. Their corresponding ylides, which were prepared by basic treatment of the sulfonium salts, reacted smoothly with a broad array of simple and chiral aldehydes to provide trans-epoxy amides in reasonable to very good yields and excellent stereoselectivities (>98 %). The obtained epoxy amides were found to be useful as synthetic building blocks. Thus, they were reduced into their corresponding epoxy alcohols and subjected to oxirane-ring-opening reactions with different types of nucleophiles.
Sarabia, Francisco,Vivar-García, Carlos,García-Castro, Miguel,García-Ruiz, Cristina,Martín-Gálvez, Francisca,Sánchez-Ruiz, Antonio,Chammaa, Samy
supporting information
p. 15190 - 15201
(2013/01/15)

Stereoselective synthesis of N,O,O,O-tetraacetyl-D-ribo-phytosphingosine, N,O,O-triacetyl-D-erythro-sphingosine and N,O,O-triacetyl sphingonine from a common chiral intermediate derived from D-mannitol
An efficient protocol for the stereoselective synthesis of tetraacetyl-D-ribo-hytosphingosine, triacetyl-D-erythro-sphingosine and triacetyl sphinganine has been devised from a common chiral intermediate derived from commercially available D-mannitol. The key steps involved are Sharpless epoxidation, Miyashita C(2) selective endo mode azide opening of 2,3-epoxy alcohol, and selective E-Wittig olefination. ARKAT-USA, Inc.
Mettu, Ravinder,Thatikonda, Narendar Reddy,Olusegun, Oladoye Sunday,Vishvakarma, Ramesh,Vaidya, Jayathirtha Rao
p. 421 - 436
(2013/11/06)

Novel fluorescent ceramide derivatives for probing ceramidase substrate specificity
Ceramidases are key regulators of cell fate. The biochemistry of different ceramidases and of their substrate ceramide appears to be complex, mainly due to specific biophysical characteristics at the water-membrane interface. In the present study, we describe the design and synthesis of a set of fluorescently labeled ceramides as substrates for acid and neutral ceramidases. For the first time we have replaced the commonly used polar NBD-dye with the lipophilic Nile Red (NR) dye. Analysis of kinetic data reveal that although both the dyes do not have any noticeable preference for the substitution at acyl or sphingosine (Sph) part in ceramide towards hydrolysis by acid ceramidase, the ceramides with acyl-substituted NBD and Sph-substituted NR dyes have been found to be a better substrate for neutral ceramidase.
Bhabak, Krishna P.,Proksch, Denny,Redmer, Susanne,Arenz, Christoph
supporting information
p. 6154 - 6161
(2012/11/07)

A practical and cost-effective synthesis of d-erythro-sphingosine from d-ribo-phytosphingosine via a cyclic sulfate intermediate
The practical and efficient synthesis of d-erythro-sphingosine from commercially available d-ribo-phytosphingosine is described-. An important feature of this synthesis is the selective transformation of the 3,4-vicinal diol of phytosphingosine into the characteristic E-allylic alcohol of sphingosine via a cyclic sulfate intermediate that contains a non-nucleophilic trifluoroacetamide protecting group. Georg Thieme Verlag Stuttgart - New York.
Lee, Yun Mi,Lee, Seokwoo,Jeon, Hongjun,Baek, Dong Jae,Seo, Jae Hong,Kim, Deukjoon,Kim, Sanghee
experimental part
p. 867 - 872
(2011/05/05)

A rapid and efficient synthesis of D-erythro-sphingosine from D-ribo-phytosphingosine
In this paper we describe the concise synthesis of D-erythro-sphingosine starting from the readily available chiral building block D-ribo- phytosphingosine. The title compound is the ubiquitous sphingolipid from which most mammalian ceramides are derived. Our work is based on the existing literature in which the same sphingoid base is used as a starting point and culminates in what we believe is the most efficient synthesis of D-erythro-sphingosine reported to date.
Van Den Berg, Richard J. B. H. N.,Van Den Elst, Hans,Korevaar, Cornelius G. N.,Aerts, Johannes M. F. G.,Van Der Marel, Gijsbert A.,Overkleeft, Herman S.
experimental part
p. 6685 - 6689
(2012/01/04)

Exploring Leishmania major Inositol Phosphorylceramide Synthase (LmjIPCS): Insights into the ceramide binding domain
The synthesis of set of ceramide analogues exploring hydrophobicity in the acyl chains and the degree and nature of hydroxylation is described. These have been assayed against the parasitic protozoan enzyme LmjIPCS. These studies showed that whilst the C-3 hydroxyl group was not essential for turnover it provided enhanced affinity. Reflecting the membrane bound nature of the enzyme a long (C13) hydrocarbon ceramide tail was necessary for both high affinity and turnover. Whilst the N-acyl chain also contributed to affinity, analogues lacking the amide linkage functioned as competitive inhibitors in both enzyme and cell-based assays. A model that accounts for this observation is proposed.
Mina, John G.,Mosely, Jackie A.,Ali, Hayder Z.,Denny, Paul W.,Steel, Patrick G.
supporting information; experimental part
p. 1823 - 1830
(2011/04/26)

Efficient silver-catalyzed regio- and stereospecific aziridination of dienes
Nitrene transfer: Unsymmetric dienes bearing a terminal hydroxy group can be regio- and stereospecifically converted into vinylaziridines upon nitrene transfer from PhINTs using a silver-based catalyst. Stoichiometric mixtures of dienes and PhINTs were employed at low catalyst loadings (0.5□%; see scheme). The method has been applied to the synthesis of (±)-sphingosine and gave good yields in a three-step procedure. Ts=4-toluenesulfonyl.
Llaveria, Josep,Beltran, Alvaro,Diaz-Requejo, M. Mar,Perez, Pedro J.,Matheu, M. Isabel,Castillon, Sergio
supporting information; experimental part
p. 7092 - 7095
(2010/11/05)

Synthesis of D/L-erythro-Sphingosine Using a Tethered Aminohydroxylation Reaction as the Key Step
A diastereoselective synthesis of racemic D/L-erythro- sphingosine is described. The approach involves employing tethered aminohydroxylation (TA) to introduce the 2-amino and 3- hydroxy functions with required stereochemistry. Georg Thieme Verlag Stuttgart.
Morales-Serna, Jose Antonio,Isabel Matheu, Yolanda Diaz M.,Castillon, Sergio
experimental part
p. 710 - 712
(2009/09/06)

Asymmetric synthesis of triacetyl-d-erythro-sphingosine and D-1-deoxyallonojirimycin via Miyashita C2 selective endo-mode azide opening of 2,3-epoxy alcohol
An efficient protocol for the asymmetric synthesis of triacetyl-d-erythro-sphingosine and D-1-deoxyallonojirimycin has been developed starting from commercially available propargyl alcohol. The key steps involved Sharpless asymmetric epoxidation and Miyashita C2 selective endo-mode azide opening of the 2,3-epoxy alcohol.
Sridhar,Srinivas,Rao, K. Rama
experimental part
p. 10701 - 10708
(2010/01/16)

An efficient and general enantioselective synthesis of sphingosine, phythosphingosine, and 4-substituted derivatives
A general and efficient protocol for the enantioselective synthesis of sphingosine, phythosphingosine, and 4-substituted derivatives was established. These compounds were obtained from a common intermediate prepared from butadiene monoepoxide by a synthet
Llaveria, Josep,Diaz, Yolanda,Matheu, M. Isabel,Castillon, Sergio
supporting information; experimental part
p. 205 - 208
(2009/06/20)

Diastereoselective nickel-catalyzed reductive couplings of aminoaldehydes and alkynylsilanes: application to the synthesis of d-erythro-sphingosine
A strategy for the nickel-catalyzed reductive coupling of α-aminoaldehydes with silyl alkynes has been developed. The process proceeds with exceptional regiocontrol and diastereoselectivity. A variety of protected serinal derivatives were examined, and Garner aldehyde afforded the highest chemical yields of an easily deprotected coupling product. Use of a C-15 alkyne allowed a direct and efficient synthesis of d-erythro-sphingosine. With this silyl alkyne of interest, coupling reactions were most efficient when trace water was employed with THF as solvent. Using this procedure, d-erythro-sphingosine was prepared by a short sequence, wherein the alkene stereochemistry, C-3 stereocenter, and the C-3-C-4 carbon-carbon bond were all efficiently installed by the key nickel-catalyzed coupling process.
Sa-ei, Kanicha,Montgomery, John
experimental part
p. 6707 - 6711
(2011/02/26)

Asymmetric synthesis of vicinal amino alcohols: Xestoaminol C, sphinganine and sphingosine
The highly diastereoselective anti-aminohydroxylation of α,β-unsaturated esters, via conjugate addition of lithium (S)-N-benzyl-N-(α-methylbenzyl)amide and subsequent in situ enolate oxidation with (+)-(camphorsulfonyl)oxaziridine, has been used as the key step in the asymmetric synthesis of N,O-diacetyl xestoaminol C (41% yield over 8 steps), N,O,O-triacetyl sphinganine (30% yield over 8 steps) and N,O,O-triacetyl sphingosine (30% yield over 7 steps). The Royal Society of Chemistry 2008.
Abraham, Elin,Davies, Stephen G.,Millican, Nicholas L.,Nicholson, Rebecca L.,Roberts, Paul M.,Smith, Andrew D.
supporting information; experimental part
p. 1655 - 1664
(2008/10/09)

SYNTHESIS OF SPHINGOSINES AND THEIR DERIVATIVES
Embodiments of the present disclosure provide for methods of making sphingosines and derivatives thereof, and the like.
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Page/Page column 20

(2008/06/13)

Asymmetric sulfur ylide based enantioselective synthesis of D-erythro-sphingosine
An asymmetric sulfur ylide reaction was employed to prepare an epoxide intermediate in a convergent manner. This epoxide was efficiently transformed into D-erythro-sphingosine.
Morales-Serna, Jose Antonio,Llaveria, Josep,Diaz, Yolanda,Matheu, M. Isabel,Castillon, Sergio
supporting information; experimental part
p. 4502 - 4504
(2009/03/12)

CATIONIC CERAMIDES, AND ANALOGS THEREOF, AND THEIR USE FOR PREVENTING OR TREATING CANCER
The present invention relates to cationic ceramides, their dihydro-analogs and aromatic analogs and their derivatives, comprising a pyridinium group. Also provided are methods for making cationic ceramides comprising a pyridinium group, and their use for treating or preventing diseases associated with cell overproliferation and sphingolipid signal transduction, such as cancer, inflammation, and stenosis. The compounds are also useful as mitochondritropic agents that are localized to mitochondria carrying with them chemical cargoes, such as drugs, or signaling molecules, such as fluorophores for probing organelle structure and functions.
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Page/Page column 71

(2008/06/13)

Efficient synthesis of D-erythro-sphingosine and D-erythro-azidosphingosine from D-ribo-phytosphingosine via a cyclic sulfate intermediate
The synthesis of naturally occurring D-erythro-sphingosine and synthetically useful D-erythro-2-azidosphingosine from commercially available D-ribo-phytosphingosine is described. An important feature of this synthesis is the selective transformation of the 3,4-vicinal diol of phytosphingosine into the characteristic E-allylic alcohol of sphingosine via a cyclic sulfate intermediate.
Kim, Sanghee,Lee, Sukjin,Lee, Taeho,Ko, Hyojin,Kim, Deukjoon
p. 8661 - 8664
(2007/10/03)

SPHINGOLIPID-DERIVED PHARMACEUTICAL COMPOSITIONS
The present invention relates to specific sphingolipids/sphingolipid derivatives as pharmaceutical compositions as well as their use in the preparation of medicaments for the treatment, prevention and/or amelioration of disorders relating to pathological processes in lipid rafts.
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Page/Page column 44 page (tiff file)

(2008/06/13)

Versatile synthetic method for sphingolipids and functionalized sphingosine derivatives via olefin cross metathesis
A highly efficient and versatile method for the synthesis of various sphingolipids, such as sphingomyelin, ceramide, sphingosine, sphingosine 1-phosphate, and functionalized sphingosine derivatives, was established by two types of combinations of the olefin cross metathesis reaction. One reaction was between the same olefin part and appropriate amino alcohols, which were prepared starting from N-Boc-L-serine, and the other was between appropriate olefins and the same amino alcohol.
Yamamoto, Tetsuya,Hasegawa, Hiroko,Hakogi, Toshikazu,Katsumura, Shigeo
p. 5569 - 5572
(2007/10/03)

Enantiodivergent synthesis of D- and L-erythro-sphingosines through Mannich-type reactions of N-benzyl-2,3-O-isopropylidene-D-glyceraldehyde nitrone
The addition of a 2-silyloxy silylketene acetal to N-benzyl-2,3-O- isopropylidene-D-glyceraldehyde nitrone (Mannich-type reaction) can be stereocontrolled to give 2S,3S,4S and 2R,3R,4S adducts as major compounds, depending on whether the reaction is activated with zinc(II) triflate or tin-(IV) chloride, respectively. The corresponding major adducts were used for preparing diastereomeric polyhydroxy-β-aminoesters that were further converted into suitable orthogonally protected enantiomeric D- and L-erythro-sphingosines.
Merino, Pedro,Jimenez, Pablo,Tejero, Tomas
p. 4685 - 4688
(2007/10/03)

Efficient and versatile synthesis of (2S,3R)-sphingosine and its 2-azido-3-O-benzylsphingosine analogue
The title compounds (1, 2) were synthesized from (2R,3S)-2-O-benzyl-3,4-O- (3′-pentylidene)-2,3,4-trihydroxybutanal (5). Installation of the E-double bond and aliphatic chain into the sphingosine base was effected by a sequence of Horner-Wadsworth-Emmons olefination of 5, conversion to allylic acetate 8, and copper-mediated Grignard coupling. The method is versatile, allowing a broad variety of aliphatic chains to be introduced in the organocuprate coupling step.
Lu, Xuequan,Bittman, Robert
p. 1873 - 1875
(2007/10/03)

Chirality transfer from guanidinium ylides to 3-alkenyl (or 3-alkynyl) aziridine-2-carboxylates and application to the syntheses of (2R,3S)-3-hydroxyleucinate and D-erythro-sphingosine
Reaction of chiral guanidinium ylides with α,β-unsaturated aldehydes gives 3-(α,β-unsaturated) aziridine-2-carboxylates in high diastereo- and enantioselectivities (up to 93% diastereomeric excess and 98% enantiomeric excess). 3-(1-Methylvinyl)- and 3-[(E)-pentadec-1-enyl]aziridine-2- carboxylates were successfully employed to prepare (2R,3S)-3-hydroxyleucinate and D-erythro-sphingosine, respectively.
Disadee, Wannaporn,Ishikawa, Tsutomu
p. 9399 - 9406
(2007/10/03)

Effective, high-yielding, and stereospecific total synthesis of D-erythro-(2R,3S)-sphingosine from D-ribo-(2S,3S,4R)-phytosphingosine
The synthesis of naturally occurring D-erythro-(2R,3S,4E)-sphingosine from commercially available D-ribo-(2S,3S,4R)-phytosphingosine is described. The key step in the reaction sequence comprises TMSI/DBN promoted regio- and stereoselective oxirane opening of intermediate 2-phenyl-4-(S)-[(1S,2S)-1,2- epoxyhexadecyl]-1,3-oxazoline followed by the in situ trans-elimination of 2-phenyl-4-(S)-[(1S,2R)-1,2-dideoxy-2-iodo-1-trimethylsilyloxyhexadecyl]-1, 3-oxazoline.
Van Den Berg, Richard J. B. H. N.,Korevaar, Cornelius G. N.,Overkleeft, Herman S.,Van Der Marel, Gijsbert A.,Van Boom, Jacques H.
p. 5699 - 5704
(2007/10/03)

A process for the synthesis of sphingosine
This invention relates to a method for the production of a sphingoid base according to formula comprising the steps of(1) dissolving a starting compound according to formula III or a salt thereof in a substantially inert solvent,(2) protecting the NH2 group with a NH2 protecting group,(3) activating C4 HR3' for an elimination reaction with C5HR4,(4) causing an elimination reaction to take place to form a double bond between the C4 and C5 carbon atom,(5) removing the NH2 protecting group.
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Page 22-23

(2010/02/08)

A practical synthesis of D-erythro-sphingosine using a cross-metathesis approach
Starting from a vinylepoxide, a short and practical synthesis of D-erythro-sphingosine is described. The key transformations are a regioselective opening of the vinylepoxide and an E-selective cross-metathesis, affording the target molecule in 5 steps and 51% overall yield.
Torssell, Staffan,Somfai, Peter
p. 1643 - 1646
(2007/10/03)

Divergent synthesis of D-erythro-sphingosine, L-threo-sphingosine, and their regioisomers
Starting from a vinyl epoxide, a divergent synthesis of four sphingosine isomers is described. The remaining four isomers can easily be synthesized using the same methodology. Although numerous syntheses of sphingosine have been published, this is the first general route leading to all eight isomers in this important compound class. The synthetic strategy relies on regioselective opening of a vinyl epoxide and a vinylaziridine in the allylic position.
Olofsson, Berit,Somfai, Peter
p. 2514 - 2517
(2007/10/03)

Synthesis of sphingosine relatives. Part-26Ψ: Synthesis of ceramide 1 {(2S, 3R, 4E)-N-[30′-(linoleoyloxy)triacontanoyl]-4- sphingenine}, a unique constituent of human skin
Ceramide 1 {(2S,3R,4E)-N-[30′-(linoleoyloxy)triacontanoyl]-4- sphingenine, 1}, a unique ceramide of human epidermal stratum corneum, was synthesized from (S)-Garner's aldehyde (2), pentadecan-15-olide (5) and linoleic acid.
Masuda, Yui,Mori, Kenji
p. 1081 - 1083
(2007/10/03)

Synthesis of Ceramide Mimics with a Pseudo Cyclic Framework
We have designed and synthesized ceramide mimics with a pseudo cyclic framework that can be converted to 'dimeric' sphingomyelins and glycosphingolipids for potential components of artificial rafts. These molecules are characterized by the presence of (i) two hydrophilic head groups, (ii) a covalently bonded hydrocarbon chain, and (iii) two untethered alkyl chains. Self-assembling of a ceramide mimic into nanorods is briefly discussed.
Suzuki, Hikokazu,Mori, Michiko,Shibakami, Motonari
p. 2163 - 2166
(2007/10/03)

Sphingomyelin analogues as inhibitors of sphingomyelinase
To search for neutral sphingomyelinase inhibitors we designed and synthesized hydrolytically stable analogues of sphingomyelin. The novel compounds 8 and 9 which were replaced the phosphodiester moiety of sphingomyelin with the carbamate moiety showed inhibitory activity with an IC50 value of μM on neutral sphingomyelinase in rat brain microsomes. Compound 8i showed a selective neutral sphingomyelinase inhibitory activity.
Taguchi, Minoru,Sugimoto, Kikuo,Goda, Ken-Ichi,Akama, Tomoko,Yamamoto, Kyoko,Suzuki, Taizo,Tomishima, Yasumitsu,Nishiguchi, Mariko,Arai, Koshi,Takahashi, Kenzo,Kobori, Takeo
p. 1963 - 1966
(2007/10/03)

Synthesis and potent antileukemic activities of N-lactylsphingosine and N-lactyldihydrosphingosine
N-(R)- and N-(S)-Lactylsphingosine and their corresponding dihydrosphingosine derivatives were synthesized. The antileukemic activities of these compounds were measured by MTT (3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide) assay in human leukemia HL-60 cells. N-(R)- and N-(S)-Lactylsphingosine displayed higher activities than N-acetylsphingosine (C2-ceramide, a well-known apoptosis inducer), and their dihydrosphingosine derivatives had slight activities.
Azuma, Hideki,Takao, Ryoko,Shikata, Keiji,Niiro, Hayato,Tachibana, Taro,Ogino, Kenji
p. 3445 - 3447
(2007/10/03)