- An Improved, Versatile, and Easily Scalable Synthesis of Sphingomyelins: Application to Stable Isotope Labeling
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With a view to make conveniently labeled mass spectrometry standards available, a set of deuterated sphingomyelins were prepared by a new expedient, flexible, robust, scalable, and high-yielding synthetic scheme starting from 2-azido-3- O -benzoylsphingos
- Blankenstein, J?rg,Le Strat, Franck,Pérard, Serge,Philippe, Nicolas,Roy, Sébastien
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supporting information
p. 2106 - 2110
(2020/08/17)
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- Α - galactose ceramide new isomer and its synthetic method
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The invention provides an alpha-galactosyl ceramide new isomer and its synthetic method. Configuration of sphingosine chain is changed to 4,5-cis double bond sphingosine chain. According to the invention, reaction steps are shortened, yield is raised, and aftertreatment and purification steps are omitted. The synthetic method can be used for total synthesis of similar glycosyl ceramide and satisfies wide range of development, research and application of different glycosyl ceramide.
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- 4,5-Cis Unsaturated α-GalCer Analogues Distinctly Lead to CD1d-Mediated Th1-Biased NKT Cell Responses
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The total synthesis of 4,5-cis unsaturated α-GalCer analogues was achieved, and their immune-response altering activity was assessed in vitro as well as in vivo in mice. Using glycosyl iodide as a glycosyl donor, construction of the sphingosine unit was shortened by four steps and single α-stereoselectivity was achieved in good yield (67%). With regard to the therapeutic use of α-GalCer, the novel analogues (1b and 1c) distinctly induced a Th1-biased cytokine response, avoiding induction of a contradictory response and overstimulation.
- Cui, Yanli,Li, Zhiyuan,Cheng, Zhaodong,Xia, Chengfeng,Zhang, Yongmin
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p. 1209 - 1215
(2015/06/25)
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- Alpha-GLYCOSYL THIOLS AND alpha-S-LINKED GLYCOLIPIDS
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The present invention relates to stereoselective methods for the preparation of α-glycosyl thiols and α-S-linked glycosylceramides.
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Page/Page column 5; Figure 2
(2010/08/07)
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- Synthesis of a 1α-C-methyl analogue of 25-hydroxyvitamin D3: interaction with a mutant vitamin D receptor Arg274Leu
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Vitamin D3 analogues have been developed for a mutant vitamin D receptor (VDR), Arg274Leu. The mutant VDR has a mutation at Arg274, which forms an important hydrogen bond with 1α-OH of 1α,25-dihydroxyvitamin D3 to anchor the ligand t
- Honzawa, Shinobu,Takahashi, Naoyuki,Yamashita, Atsushi,Sugiura, Takayuki,Kurihara, Masaaki,Arai, Midori A.,Kato, Shigeaki,Kittaka, Atsushi
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scheme or table
p. 7135 - 7145
(2009/12/06)
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- First total synthesis of theopederin B
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Total synthesis of theopederin B, isolated from marine sponge, was accomplished by coupling pederic acid, as the left half, with trioxodecaline amine as the right half. Key reactions for synthesizing the amine were SmI2-promoted Reformatsky rea
- Nishii, Yoshinori,Higa, Tsuyoshi,Takahashi, Shunya,Nakata, Tadashi
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scheme or table
p. 3597 - 3601
(2009/09/28)
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- A practical and enantiospecific conversion of d-galactose to a substituted α,β-unsaturated δ-lactone synthon
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A multi-gram synthesis of a substituted α,β-unsaturated δ-lactone synthon, 1, was developed from commercially available d-galactose. The use of a Horner-Wadsworth-Emmons reaction was able to furnish, with Z selectivity, the enone ester that spontaneously
- Stephens, Benjamin E.,Liu, Fei
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p. 9116 - 9119
(2008/09/17)
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- Effects of α-alkoxy substitution and conformational constraints on 6-exo radical cyclizations of hydrazones via reversible thiyl and stannyl additions
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Access to multifunctional hydrazones of relevance to dysiherbaine synthesis studies is described. Subsequent radical cyclizations of multifunctional hydrazones via a Si- and C-linked tethering strategy are shown to function effectively in 6-exo fashion. C
- Friestad, Gregory K.,Mathies, Alex K.
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p. 9373 - 9381
(2008/02/10)
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- The dioxanone approach to (2S,3R)-2-C-methylerythritol 4-phosphate and 2,4-cyclodiphosphate, and various MEP analogues
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(Chemical Equation Presented) Efficient syntheses of the non-mevalonate pathway intermediates 2-C-methylerythritol 4-phosphate (MEP) and 2-C-methylerythritol 2,4-cyclodiphosphate (ME-2,4-cycloPP), as well as the parent tetrol 2-C-methylerythritol, in enantiopure form from (2S,4R)-cis-2-phenyl-4-tert-butyldimethylsilyloxy-1,3-dioxan-5-one are reported. The 2S configuration of the C-methyl group was installed by highly axial-face selective addition of CH3MgBr (20:1) to the chiral dioxanone carbonyl group. Primary selective monophosphorylation and 2,4-bis-phosphorylation, followed by desilation and hydrogenolysis to the free mono-and diphosphates, and, in the latter case, cyclization to form the eight-membered phosphoryl anhydride, afforded MEP and ME-2,4-cycloPP in good yields. The C2 epimeric analogues, 2-C-methylthreitol and its 4-phosphate, were accessed by LiAlH 4 reduction of the cis,cis epoxide of (2S,4R)-4-tert- butyldimethylsilyloxymethyl-5-methylene-2-phenyl-1,3-dioxane, primary-selective phosphorylation, and cleavage of the silyl, benzylidene, and benzyl protecting groups. Regioselective cleavage of the acetal ring of 1,3-benzylidene 2-C-methylerythritol silyl ether by ozonolysis afforded a 1,2,3-triol 3-monobenzoate intermediate that was converted to the novel amino sugar, 1-amino-1-deoxy-2-C-methylerythritol.
- Lagisetti, Chandraiah,Urbansky, Marek,Coates, Robert M.
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p. 9886 - 9895
(2008/03/28)
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- Synthesis of Enantiopure 2-C-Methyl-D-erythritol 4-Phosphate and 2,4-Cyclodiphosphate from D-Arabitol
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(Equation presented) Two key intermediates of the newly discovered mevalonate-independent pathway for isoprenoid biosynthesis were prepared. Optically pure 2-C-methyl-D-erythritol 4-phosphate and 2,4-cyclodiphosphate were chemically synthesized from D-arabitol using a convenient benzylidene and tert-butyldimethylsilyl protection of polyhydroxylated intermediates. The new scheme offers a straightforward route to analogues and labeled forms.
- Urbansky, Marek,Davis, Chad E.,Surjan, Jacob D.,Coates, Robert M.
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p. 135 - 138
(2007/10/03)
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- The total syntheses of D-erythro-sphingosine, N-palmitoylsphingosine (ceramide), and glucosylceramide (cerebroside) via an azidosphingosine analog
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The total synthesis of D-erythro-sphingosine (9) was performed by a chirospecific method starting from D-galactose via an azidosphingosine intermediate to give highly homogeneous ( > 99.9% C18:1) sphingosine base (9) which contained no observable olefin isomerization by product and was demonstrated to be optically pure by a novel method utilizing Mosher's acid. Ceramide (10) was prepared from this sphingosine (9) with highly homogeneous (99.8% C16:0) palmitic acid by two methods. The cerebroside glucosylceramide (23) was the next sphingolipid in this series to be synthesized in a highly homogeneous form. These three sphingolipids are currently being used for biophysical studies of the structures of their hydrated bio-molecular assemblies.
- Duclos Jr., Richard I
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p. 111 - 138
(2007/10/03)
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- Radical cyclization of oxime ethers derived from monosaccharides aiming at the synthesis of dysiherbaine and related stereoisomers
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Stannyl radical-mediated cyclization of oxime ethers (6), (14), (22), and (29) derived from glucose and galactose afforded the cyclized aminosugar derivatives (7), (8), (15, 16 and 17), (23), (24), and (30, 31 and 32) which would serve as key intermediates for the synthesis of dysiherbaine and its isomers.
- Naito, Takeaki,Nair,Nishiki, Akiyoshi,Yamashita, Kazuhiko,Kiguchi, Toshiko
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p. 2611 - 2615
(2007/10/03)
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- SYNTHESES OF D-ERYTHRO-1-DEOXYDIHYDROCERAMIDE-1-SULFONIC ACID AND PHOSPHONOSPHINGOGLYCOLIPID FOUND IN MARINE ORGANISM VIA A COMMON PRECURSOR
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D-Erythro-1-deoxydihydroceramide-1-sulfonic acid, isolated from alkali-stable hydrogenated lipids in a non-photosynthetic marine diatom, Nitzschia alba, and (2S,3R)-N-palmitoyl-1-O--β-D-galactopyranosyl>-D-sphingosine, found in marine snail Turbo cornutus were synthesized via a common precursor (10) starting from galactose.
- Ohashi, Kinji,Kosai, Shunji,Arizuka, Mitsuo,Watanabe, Takashi,Yamagiwa, Yoshiro,et al.
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p. 2557 - 2570
(2007/10/02)
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- SYNTHESIS OF D-ERYTHRO-1-DEOXYDIHYDROCERAMIDE-1-SULFONIC ACID
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New D-erythro-1-deoxydihydroceramide-1-sulfonic acid, isolated from alkali-stable lipids in a non-photosynthetic marine diatom Nitzschia alba, was synthesized from galactose as a chiral precursor using the Hanessian-Hullar reaction as the key step in the
- Ohashi, Kinji,Yamagiwa, Yoshiro,Kamikawa, Tadao,Kates, Morris
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p. 1185 - 1188
(2007/10/02)
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- Synthesis of Sphingosines, 4. - Synthesis of erythro-Sphingosines via Their Azido Derivatives
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The 2,4-O-protected D-threoses 3a and 3b were obtained from D-galactose and D-xylose, respectively, in two-step procedures.Wittig reaction in the presence of an excess of lithium bromide afforded the trans-enetriols 4aA, 4aB, and 4bA.Triflate activation of the unprotected 2-hydroxy group, azide group introduction, and cleavage of the O-protective groups yielded the azidosphingosines 6A,B which provide after azide group reduction the D-erythro-sphingosines 7A,B.For the glycosphingolipid synthesis through azidosphingosine glycosylation, compound 6A was transformed by 1-O tritylation, 3-O protection, and subsequent 1-O detritylation into the 3-O-protected azidosphingosines 11α-11γ.
- Zimmermann, Peter,Schmidt, Richard R.
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p. 663 - 668
(2007/10/02)
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- SYNTHESIS OF D-ERYTHRO-SPHINGOSINES
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2,4-Di-O-protected D-threose, readily available from D-galactose, is a versatile intermediate for D-erythro-sphingosine syntheses via trans-selective Wittig reaction, azide introduction at the unprotected hydroxylic group, and subsequent azide reduction.
- Schmidt, Richard R.,Zimmermann, Peter
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p. 481 - 484
(2007/10/02)
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- The Biosynthesis of Thiamine. Syntheses of -1-Deoxy-D-threo-2-pentulose and Incorporation of this Sugar in Biosynthesis of Thiazole by Escherichia coli Cells
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Non-growing, washed cells of Escherichia coli, depressed for the synthesis of thiamine, were incubated in the presence of -1-deoxy-D-threo-2-pentulose (9) in a medium containing the pyrimidine moiety of thiamine, L-tyrosine, and glucose.The thiamine thus biosynthesized was extracted and cleaved to give 5-(2-hydroxyethyl)-4-methylthiazole (HET) which was examined as the trifluoroacetate derived by electron-impact mass spectrometry.The distribution of the label in the fragments indicated that the pentulose (9) was a precursor of the C5-chain of HET without C-C bond cleavage.Several routes to 1-deoxypentuloses are described.Condensation of 2,4-O-benzylidene-D-threose (23) with trideuteriomethylmagnesium iodide gave the protected 1-deoxypentitols (24) and (25).Brominolysis of the mixed dibutylstannylidenes then afforded -3,4-O-benzylidene-1-deoxy-D-threo-2-pentulose (26), which was converted into the free sugar (9) by acidic hydrolysis. 1-Deoxy-D-erythro-2-pentulose was prepared in similar manner.Condensation of 2-(-methyl)-1,3-dithian with 2,3-O-isopropylidene-D-glyceraldehyde, followed by a C-3 epimerization step also led, after deprotection, to a mixture of -1-deoxy-D-erythro- and -1-deoxy-D-threo-2-pentulose, (5) and (6).
- David, Serge,Estramareix, Bernard,Fischer, Jean-Claude,Therisod, Michel
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p. 2131 - 2138
(2007/10/02)
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