- A diversity oriented synthesis of D-erythro-sphingosine and siblings
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An efficient building block-based synthetic protocol has been developed for the synthesis of 3-ketosphingoids with various chain lengths using cross metathesis of a Garner's aldehyde-derived α,β-unsaturated ketone as the key step. Stereoselective reduction of the biomimetic precursors thus obtained provided D-erythro-sphingosine and truncated anaogues in good overall yields.
- Ghosh, Amrita,Chattopadhyay, Shital K.
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Read Online
- Synthesis and potent antileukemic activities of N-lactylsphingosine and N-lactyldihydrosphingosine
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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
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Read Online
- Efficient synthesis of sphingosine-1-phosphonate and homo-sphingosine-1-phosphonate
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Sphingosine can be selectively transformed into 2-N,3-O-protected 1-O-mesyl derivative 8. Transformation into the bromide, Michaelis-Arbusov reaction with trimethyl phosphite, and then removal of all protective groups with LiOH afforded sphingosine-1-phosphonate (4) in high overall yield. Chain extension of 8 with KCN and ensuing reduction led to homosphingosine derivative 10 and also to homo-1-deoxysphingosine (5). 1-O-Mesylation of 10 led via the same sequence of reactions finally to homo-sphingosine-1-phosphonate (6).
- Tarnowski, Andrej,Baer, Thomas,Schmidt, Richard R.
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Read Online
- 4'-HALOGEN CONTAINING NUCLEOTIDE AND NUCLEOSIDE THERAPEUTIC COMPOSITIONS AND USES RELATED THERETO
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Disclosed are halogen containing nucleotide and nucleoside therapeutic compositions and uses related thereto. In certain embodiments, the disclosure relates to the treatment or prophylaxis of viral infections. Such viral infections can include tongaviridae, bunyaviridae, arenaviridae, coronaviridae, flaviviridae, picornaviridae, Eastern, Western, and Venezuelan Equine Encephalitis (EEE, WEE and VEE, respectively), Chikungunya fever (CHIK), Ebola, Influenza, RSV, and Zika virus infections.
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Page/Page column 308
(2021/07/10)
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- Preparation of Nitrogen Analogues of Ceramide and Studies of Their Aggregation in Sphingomyelin Bilayers
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Ceramides can regulate biological processes probably through the formation of laterally segregated and highly packed ceramide-rich domains in lipid bilayers. In the course of preparation of its analogues, we found that a hydrogen-bond-competent functional group in the C1 position is necessary to form ceramide-rich domains in lipid bilayers [ Matsufuji; et al. Langmuir 2018 ]. Hence, in the present study, we newly synthesized three ceramide analogues: CerN3, CerNH2, and CerNHAc, in which the 1-OH group of ceramide is substituted with a nitrogen functionality. CerNH2 and CerNHAc are capable of forming hydrogen bonds in their headgroups, whereas CerN3 is not. Fluorescent microscopy observation and differential scanning calorimetry analysis disclosed that these ceramide analogues formed ceramide-rich phases in sphingomyelin bilayers, although their thermal stability was slightly inferior to that of normal ceramides. Moreover, wide-angle X-ray diffraction analysis showed that the chain packing structure of ceramide-rich phases of CerNHAc and CerN3 was similar to that of normal ceramide, while the CerNH2-rich phase showed a slightly looser chain packing due to the formation of CerNH3+. Although the domain formation of CerN3 was unexpected because of the lack of hydrogen-bond capability in the headgroup, it may become a promising tool for investigating the mechanistic link between the ceramide-rich phase and the ceramide-related biological functions owing to its Raman activity and applicability to click chemistry.
- Yasuda, Hiroki,Torikai, Kohei,Kinoshita, Masanao,Sazzad, Md. Abdullah Al,Tsujimura, Koya,Slotte, J. Peter,Matsumori, Nobuaki
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p. 12438 - 12446
(2021/11/01)
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- Liposomal FRET Assay Identifies Potent Drug-Like Inhibitors of the Ceramide Transport Protein (CERT)
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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
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p. 16616 - 16621
(2020/11/30)
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- N-AS-triggered SPMs are direct regulators of microglia in a model of Alzheimer’s disease
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Sphingosine kinase1 (SphK1) is an acetyl-CoA dependent acetyltransferase which acts on cyclooxygenase2 (COX2) in neurons in a model of Alzheimer’s disease (AD). However, the mechanism underlying this activity was unexplored. Here we show that N-acetyl sphingosine (N-AS) is first generated by acetyl-CoA and sphingosine through SphK1. N-AS then acetylates serine 565 (S565) of COX2, and the N-AS-acetylated COX2 induces the production of specialized pro-resolving mediators (SPMs). In a mouse model of AD, microglia show a reduction in N-AS generation, leading to decreased acetyl-S565 COX2 and SPM production. Treatment with N-AS increases acetylated COX2 and N-AS-triggered SPMs in microglia of AD mice, leading to resolution of neuroinflammation, an increase in microglial phagocytosis, and improved memory. Taken together, these results identify a role of N-AS in the dysfunction of microglia in AD.
- Bae, Jae-sung,Choi, Min-Koo,Han, Seung Hoon,Jin, Hee Kyung,Kim, Hee-Jin,Kim, Seung Hyun,Lee, Ju Youn,Park, Cheol-Min,Park, Min Hee,Schuchman, Edward H.,Song, Im-Sook,Yu, Eunsoo
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- 4'-HALOGEN CONTAINING NUCLEOTIDE AND NUCLEOSIDE THERAPEUTIC COMPOSITIONS AND USES RELATED THERETO
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Disclosed are halogen containing nucleotide and nucleoside therapeutic compositions and uses related thereto. In certain embodiments, the disclosure relates to the treatment or prophylaxis of viral infections. Such viral infections can include tongaviridae, bunyaviridae, arenaviridae, coronaviridae, flaviviridae, picornaviridae, Eastern, Western, and Venezuelan Equine Encephalitis (EEE, WEE and VEE, respectively), Chikungunya fever (CHIK), Ebola, Influenza, RSV, and Zika virus infections.
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Page/Page column 288
(2019/10/01)
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- Enantioselective Synthesis of Aminodiols by Sequential Rhodium-Catalysed Oxyamination/Kinetic Resolution: Expanding the Substrate Scope of Amidine-Based Catalysis
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Regio- and stereoselective oxyamination of dienes through a tandem rhodium-catalysed aziridination–nucleophilic opening affords racemic oxazolidinone derivatives, which undergo a kinetic resolution acylation process with amidine-based catalysts (ABCs) to achieve s values of up to 117. This protocol was applied to the enantioselective synthesis of sphingosine.
- Guasch, Joan,Giménez-Nueno, Irene,Funes-Ardoiz, Ignacio,Bernús, Miguel,Matheu, M. Isabel,Maseras, Feliu,Castillón, Sergio,Díaz, Yolanda
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supporting information
p. 4635 - 4642
(2018/03/05)
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- NUCLEOTIDE AND NUCLEOSIDE THERAPEUTIC COMPOSITIONS AND USES RELATED THERETO
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This disclosure relates to nucleotide and nucleoside therapeutic compositions and uses in treating infectious diseases, viral infections, and cancer, where the base of the nucleotide or nucleoside contains at least one thiol, thione or thioether.
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Page/Page column 66
(2017/07/14)
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- NUCLEOTIDE AND NUCLEOSIDE THERAPEUTIC COMPOSITIONS AND USES RELATED THERETO
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This disclosure relates to nucleotide and nucleoside therapeutic compositions and uses in treating infectious diseases, viral infections, and cancer, where the base of the nucleotide or nucleoside contains at least one thiol, thione or thioether.
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Page/Page column 143; 144
(2017/09/27)
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- ALKYNE CONTAINING NUCLEOTIDE AND NUCLEOSIDE THERAPEUTIC COMPOSITIONS AND USES RELATED THERETO
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This disclosure relates to nucleotide and nucleoside therapeutic compositions and uses in treating infectious diseases, viral infections, and cancer, where the base of the nucleotide or nucleoside contains at least one thiol, thione or thioether.
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Page/Page column 307; 308
(2017/12/09)
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- NUCLEOTIDE AND NUCLEOSIDE THERAPEUTICS COMPOSITIONS AND USES RELATED THERETO
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This disclosure relates to nucleotide and nucleoside therapeutic compositions and uses in treating infectious diseases, viral infections, and cancer, where the base of the nucleotide or nucleoside contains at least one thiol, thione or thioether.
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Page/Page column 261
(2016/09/26)
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- Studies on the inhibition of sphingosine-1-phosphate lyase by stabilized reaction intermediates and stereodefined azido phosphates
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Two kinds of inhibitors of the PLP-dependent enzyme sphingosine-1-phosphate lyase have been designed and tested on the bacterial (StS1PL) and the human (hS1PL) enzymes. Amino phosphates 1, 12, and 32, mimicking the intermediate aldimines of the catalytic process, were weak inhibitors on both enzyme sources. On the other hand, a series of stereodefined azido phosphates, resulting from the replacement of the amino group of the natural substrates with an azido group, afforded competitive inhibitors in the low micromolar range on both enzyme sources. This similar behavior represents an experimental evidence of the reported structural similarities for both enzymes at their active site level. Interestingly, the anti-isomers of the non-natural enantiomeric series where the most potent inhibitors on hS1PL.
- Sanllehí, Pol,Abad, José-Luís,Bujons, Jordi,Casas, Josefina,Delgado, Antonio
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supporting information
p. 905 - 915
(2016/08/24)
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- NUCLEOTIDE AND NUCLEOSIDE COMPOSITIONS AND USES RELATED THERETO
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This disclosure relates to nucleotide and nucleoside therapeutic compositions and uses in treating infectious diseases, viral infections, and cancer, where the base of the nucleotide or nucleoside contains at least one thiol, thione or thioether.
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Page/Page column 212; 213
(2015/03/28)
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- Synthesis of a panel of carbon-13-labelled (glyco)sphingolipids
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The synthesis of a focussed library of sphingolipids differing in the number and position of 13C labels is described. The synthesised sphingolipids differ in substitution at both the sphingosine amine (either palmitoylated or unmodified) and the sphingosine primary hydroxyl (unmodified or glycosylated). Moreover, 13C atoms are incorporated into either the sphingosine or the palmitate moiety, or both. This set of compounds is intended for use in relative quantitative lipidomics studies to gain insight into sphingolipid metabolism in healthy and diseased (lysosomal storage disorders) patients and animal models. The synthesis of a focussed library of sphingolipids differing in the number and position of 13C labels is described. 13C atoms are incorporated into either the sphingosine or the palmitate moiety, or both. This set of compounds is intended for use in relative quantitative lipidomics studies to gain insight into sphingolipid metabolism.
- Wisse, Patrick,Gold, Henrik,Mirzaian, Mina,Ferraz, Maria J.,Lutteke, Ginger,Van Den Berg, Richard J. B. H. N.,Van Den Elst, Hans,Lugtenburg, Johan,Van Der Marel, Gijsbert A.,Aerts, Johannes M. F. G.,Codée, Jeroen D. C.,Overkleeft, Herman S.
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p. 2661 - 2677
(2015/04/27)
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- NUCLEOTIDE AND NUCLEOSIDE THERAPEUTIC COMPOSITIONS AND USES RELATED THERETO
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This disclosure relates to nucleotide and nucleoside therapeutic compositions and uses related thereto. In certain embodiments, the disclosure relates to halogenated nucleosides optionally conjugated to a phosphorus oxide or pharmaceutically acceptable salts thereof. In certain embodiments, the disclosure relates to conjugate compounds or pharmaceutically acceptable salts thereof comprising an amino acid ester or a sphingolipid or derivative linked by a phosphorus oxide to a nucleotide or nucleoside. In certain embodiments, the disclosure contemplates pharmaceutical compositions comprising these compounds for uses in treating infectious diseases, viral infections, and cancer.
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Page/Page column 181
(2014/08/20)
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- CAGED CERAMIDE-1-PHOSPHATE DERIVATIVES
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The invention relates to novel caged ceramide 1-phosphate (C1P) and the method of using them for delivering C1P intracellularly in vitro and in vivo, for research and therapeutic purposes.
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Page/Page column 34-36
(2011/06/11)
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- Exploring Leishmania major Inositol Phosphorylceramide Synthase (LmjIPCS): Insights into the ceramide binding domain
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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.
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p. 1823 - 1830
(2011/04/26)
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- A properly protected sphingosine acceptor for helferich glycosylation
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The synthesis and some examples of glycosylations of a properly protected sphingosine is presented. This compound is suitable for the preparation of glycosphingolipids. It has been used for the synthesis of -mannosylceramide and sulfatide exploiting the anchimeric assistance to address the stereochemistry of the glycosidic bond.
- Michieletti, Mario,Sillani, Laura,Panza, Luigi
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scheme or table
p. 2609 - 2612
(2010/02/28)
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- Caged ceramide 1-phosphate analogues: Synthesis and properties
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(Chemical Equation Presented) Sphingolipid phosphate analogues bearing 7-(diethylamino)-coumarin (DECM) and 4-bromo-5-hydroxy-2-nitrobenzhydryl (BHNB) groups in a photolabile ester bond were synthesized. The ability of the "caged" ceramide 1-phosphate analogues to release the bioactive parent molecule upon irradiation at 400-500 nm was demonstrated by stimulation of macrophage cell proliferation. 2009 American Chemical Society.
- Lankalapalli, Ravi S.,Ouro, Alberto,Arana, Lide,Gomez-Munoz, Antonio,Bittman, Robert
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supporting information; experimental part
p. 8844 - 8847
(2010/03/01)
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- Practical syntheses of sphingosine-1-phosphate and analogues
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Sphingosine-1-phosphate (S1P, 1) is a bioactive sphin- golipid metabolite involved in a variety of critical cellular processes including proliferation, survival, and migration. For this reason the stereoselective syntheses of S1P and analogues are of great interest. Based on L-serine as source of chirality we achieved practical routes to prepare S1P (1) and the aryl group containing analogues 3 and 4 in fair amounts. The crucial stages of the syntheses are: introduction of the required side chain by addition of appropriate organometal- lics to Garner's aldehyde and conversion of the primary alcohols into the corresponding phosphates. Georg Thieme Verlag Stuttgart.
- Blot, Virginie,Jacquemard, Ulrich,Reissig, Hans-Ulrich,Kleuser, Burkhard
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experimental part
p. 759 - 766
(2009/07/19)
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- A concise and scalable synthesis of high enantiopurity (-)-d-erythro- sphingosine using peptidyl thiol ester-boronic acid cross-coupling
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A short and efficient synthesis of high enantiopurity (-)-D-erythro- sphingosine has been achieved in 71% yield over 6 steps from N-BOC-L-serine. The key steps are high yield, racemization-free, palladium-catalyzed, copper(I)-mediated coupling of the thiophenyl ester of N-Boc-O-TBS L-serine with E-1-pentadecenyl boronic acid and the highly diastereoselective reduction of the resulting peptidyl ketone with LiAI(O-t-Bu)3H. By using this concise route (-)-D-erythro-sphingosine can be prepared on large scale and in high enantio- and diastereopurity (ee >99%, de up to 99%).
- Yang, Hao,Liebeskind, Lanny S.
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p. 2993 - 2995
(2008/02/09)
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- Enantiodivergent synthesis of D- and L-erythro-sphingosines through Mannich-type reactions of N-benzyl-2,3-O-isopropylidene-D-glyceraldehyde nitrone
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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
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p. 4685 - 4688
(2007/10/03)
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- Versatile synthetic method for sphingolipids and functionalized sphingosine derivatives via olefin cross metathesis
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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
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p. 5569 - 5572
(2007/10/03)
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- Synthesis of sphingosine-1-phosphonate and homosphingosine-1-phosphonate
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In the first approach to homosphingosine-1-phosphonate, D-glucofuranose was selectively deoxygenated at C-5. Bond cleavage between C-1 and C-2 afforded a 5-deoxy-D-threopentose intermediate. (E)-Selective Wittig reaction with a C 14-chain gave a C19-intermediate, which was readily transformed into homosphingosine. Formation of a cyclic urethane containing the 3-amino and the 4-hydroxy group of the C19-intermediate permitted regioselective introduction of the phosphonate group at C-1, thus affording the target molecule after deprotection. In a second and shorter route, C 18-sphingosine was converted to a cyclic urethane containing the 2-amino and the 3-hydroxy group of the C18-chain. C1-Chain extension by a hydroxymethyl group by introduction of cyanide led to the same C19 cyclic urethane as obtained in the first route. Similarly, the C18 cyclic urethane led to the other target molecule, namely sphingosine-1-phosphonate. The third and shortest route to homosphingosine-1- phosphonate could be based on regioselective 1-O-tosylation of 1,2,3-(trihydroxy)octadec-4-ene. Transformation into a 1,2-epoxide, then combination of C1-chain extension and introduction of a phosphonate group with methylphosphonate as reagent, and finally azide introduction, led after functional group liberation to the target molecule. As shown, also truncated derivatives are readily accessible by this route. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.
- Tarnowski, Andrej,Retz, Oliver,Baer, Thomas,Schmidt, Richard R.
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p. 1129 - 1141
(2007/10/03)
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- Synthesis and biological properties of novel sphingosine derivatives
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Sphingosine-1-phosphate (S-1P) derivatives such as threo-(2S,3S)-analogues, which are C-3 stereoisomers of natural erythro-(2S,3R)-S-1P, have been synthesized starting from l-serine or (1S,2S)-2-amino-1-aryl-1,3-propanediols (6). threo-(1S,2R)-2-Amino-1-aryl-3-bromopropanols (HBr salt) have also been prepared from 6. The threo-S-1Ps and the threo-amino-bromide derivatives have shown potent inhibitory activity against Ca2+ ion mobilization in HL60 cells induced by erythro-S-1P, suggesting that these compounds would compete with cell surface EDG/S1P receptors.
- Murakami, Teiichi,Furusawa, Kiyotaka,Tamai, Tadakazu,Yoshikai, Kazuyoshi,Nishikawa, Masazumi
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p. 1115 - 1119
(2007/10/03)
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- A process for the synthesis of sphingosine
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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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- Cross metathesis route in sphingomyelin synthesis
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Cross metathesis reaction of short chain Boc sphingosine using Grubbs' 2nd generation catalyst proceeded in stereoselective manner to afford Boc sphingosine in good yield. An efficient synthesis of sphingomyelin was achieved from the obtained Boc sphingos
- Hasegawa, Hiroko,Yamamoto, Tetsuya,Hatano, Sho,Hakogi, Toshikazu,Katsumura, Shigeo
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p. 1592 - 1593
(2007/10/03)
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- Syntheses of sphingosine-1-phosphate stereoisomers and analogues and their interaction with EDG receptors.
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Sphingosine-1-phosphate (S1P) is considered to be an important regulator of diverse biological processes acting as a natural ligand to EDG receptors. As a preliminary study to develop potent and selective agonist and antagonist for EDG receptors, we report synthesis of S1P stereoisomers and analogues and their binding affinities to EDG-1, -3, and -5.
- Lim, Hyun Suk,Oh, Yong Seok,Suh, Pann Ghill,Chung, Sung Kee
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p. 237 - 240
(2007/10/03)
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- Synthesis of Ceramide Mimics with a Pseudo Cyclic Framework
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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
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p. 2163 - 2166
(2007/10/03)
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- A simple and low cost synthesis of D-erythro-sphingosine and D-erythro-azidosphingosine from D-ribo-phytosphingosine: Glycosphingolipid precursors
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D-erythro-Sphingosine (1) and D-erythro-2-azidosphingosine (2) are both prepared from commercially available and cheap D-ribo-phytosphingosine (3) in a yield of 58% and 70%, respectively. A key transformation in the synthesis of D-erythro-sphingosine (1) is the palladium catalyzed regiospecific reduction of the Z-enol triflate 9. A crucial step in the synthesis of azidosphingosine 2 comprises a regio- and stereoselective in situ trans-elimination of the 4-O-triflate of azidophytosphingosine 13.
- Van Den Berg, Richard J.B.H.N.,Korevaar, Cornelis G.N.,Van Der Marel, Gijsbert A.,Overkleeft, Herman S.,Van Boom, Jacques H.
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p. 8409 - 8412
(2007/10/03)
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- Efficient stereodivergent synthesis of erythro- and threo-sphingosines: Unprecedented reversal of the stereochemistry in the addition
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A convenient diastereoselective synthesis of D-erythro- and L-threo-sphingosine derivatives is described. L-Serine-derived aldehyde (Garner's aldehyde) (2) was treated with 1-alkenyl-zirconocene chlorides (3) in the presence of ZnBr2 in THF to give the natural erythro-(anti-) isomers with high diastereoselectivity (anti/syn=12-20:1). In contrast, reaction of 2 with 1-alkenyl-ethyl-zinc, prepared from 3 and Et2Zn, in CH2Cl2 gave the unnatural threo-(syn-) isomers predominantly (anti/syn=1:12-15).
- Murakami, Teiichi,Furusawa, Kiyotaka
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p. 9257 - 9263
(2007/10/03)
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- Stereoselective synthesis of D-erythro-sphingosine and L-lyxo-phytosphingosine
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An alternative synthetic route to D-erythro-sphingosine and L-lyxo-phytosphingosine was developed, utilizing chiral β-lactam 3 obtained from D-(-)-tartaric acid as a starting material.
- Nakamura, Tsuyoshi,Shiozaki, Masao
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p. 9087 - 9092
(2007/10/03)
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- An alternative synthesis of D-erythro-sphingosine and L-lyxo-phytosphingosine
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Chiral β-lactam 1 obtained from D-(-)-tartaric acid was converted to a D-erythro-sphingosine equivalent 7 in 35% yield, without yielding a 4Z-geometrical isomer, and L-lyxo-phytosphingosine 8 in 45% yield, respectively.
- Nakamura, Tsuyoshi,Shiozaki, Masao
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p. 9063 - 9064
(2007/10/03)
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- Synthesis and evaluation of a photolyzable derivative of sphingosine 1-phosphate-caged SPP
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The synthesis of a photolyzable sphingosine 1-phosphate derivative is reported via the reaction of N-(tert-butoxycarbonyl)-2-N,3-O-isopropylidenesphingosine 7 and bis(α-methyl-o-nitrobenzyl) N,N-diisopropylphosphoramidite. Stimulation of DNA synthesis upon illumination of caged SPP-loaded cells is also described.
- Qiao, Lixin,Kozikowski, Alan P.,Olivera, Ana,Spiegel, Sarah
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p. 711 - 714
(2007/10/03)
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- An Efficient and Stereoselective Synthesis of D-erythro-Sphingosine
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A highly stereoselective 3-step synthesis, leading in 81percent overall yield to D-erythro-sphingosine (8), is described.Several further examples for the nucleophilic addition to the serinal derivative 1 are given.
- Radunz, Hans-Eckart,Devant, Ralf M.,Eiermann, Volker
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p. 1103 - 1106
(2007/10/02)
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