124751-19-5Relevant academic research and scientific papers
Stereospecific C-Glycosylation by Mizoroki–Heck Reaction: A Powerful and Easy-to-Set-Up Synthetic Tool to Access α- and β-Aryl-C-Glycosides
Mabit, Thibaud,Siard, Aymeric,Legros, Frédéric,Guillarme, Stéphane,Martel, Arnaud,Lebreton, Jacques,Carreaux, Fran?ois,Dujardin, Gilles,Collet, Sylvain
, p. 14069 - 14074 (2018)
A stereospecific Mizoroki–Heck cross-coupling of differently substituted glycals with haloarenes resulting in the exclusive formation of either α- or β-aryl-C-glycosides depending solely on the configuration at C3 was achieved. The reaction was easy to set up because no specific precautions were required concerning moisture or oxygen, and it proceeded by a chirality transfer from C3 to C1. After optimization of cross-coupling conditions, various prepared glycals (7 examples) and arenes (10 examples) were tested, leading stereospecifically to the corresponding aryl-C-glycosides with a carbonyl group at C3, thus opening up new horizons for the total synthesis of glycosylated natural products.
Total Synthesis of the Congested, Bisphosphorylated Morganella morganii Zwitterionic Trisaccharide Repeating Unit
Keith, D. Jamin,Townsend, Steven D.
, p. 12939 - 12945 (2019/08/22)
Zwitterionic polysaccharides (ZPSs) activate T-cell-dependent immune responses by major histocompatibility complex class II presentation. Herein, we report the first synthesis of a Morganella morganii ZPS repeating unit as an enabling tool in the synthesis of novel ZPS materials. The repeating unit incorporates a 1,2-cis-α-glycosidic bond; the problematic 1,2-trans-galactosidic bond, Gal-β-(1 → 3)-GalNAc; and phosphoglycerol and phosphocholine residues which have not been previously observed together as functional groups on the same oligosaccharide. The successful third-generation approach leverages a first in class glycosylation of a phosphoglycerol-functionalized acceptor. To install the phosphocholine unit, a highly effective phosphocholine donor was synthesized.
General Strategy for Stereoselective Synthesis of β- N-Glycosyl Sulfonamides via Palladium-Catalyzed Glycosylation
Dai, Yuanwei,Zheng, Jianfeng,Zhang, Qiang
supporting information, p. 3923 - 3927 (2018/07/21)
A highly efficient and mild glycosylation reaction between 3,4-O-carbonate glycal and N-tosyl functionalized aliphatic and aromatic amines via palladium-catalyzed decarboxylative allylation is disclosed. A wide range of highly functionalized 2,3-unsaturat
Synthesis and biological evaluation of α-galactosylceramide analogues with heteroaromatic rings and varying positions of a phenyl group in the sphingosine backbone
Kim, Yongju,Oh, Keunhee,Song, Heebum,Lee, Dong-Sup,Park, Seung Bum
, p. 7100 - 7109 (2013/10/01)
We designed and synthesized seven α-GalCer analogues with a pyrazole moiety and varying positions of a phenyl group in the sphingosine backbone to polarize cytokine secretion. On the basis of in vitro and in vivo biological evaluations, we found that anal
Substituent effects on the SmI2/Pd(0)-promoted carbohydrate ring-contraction of 5-alkynylpyranosides
Aurrecoechea, José M.,Gil, Jesús H.,López, Beatriz
, p. 7111 - 7121 (2007/10/03)
The effect of substituents on the reactivity and stereoselectivity of the SmI2/Pd(0)-promoted ring-contraction of 5-alkynylpyranosides has been examined using substrates substituted only at selected positions. While formation of 2-ethynylcyclopentanols takes place efficiently, an internal alkyne did not afford the expected product. The presence of peripheral alkoxy substituents leads to variable stereoselectivities that depend on the number and orientation of such groups. Thus, an isolated OBn substituent at C(3) (carbohydrate numbering) exerts a significant stereochemical control while additional substitution with the same group at C(4) either enhances or drastically reduces stereoselectivity depending on its orientation (α or β, respectively).
Direct carbohydrate to carbocycle conversions via intramolecular allylation with Et2Zn/Pd(0)
Aurrecoechea, José M.,Arrate, Mónica,Gil, Jesús H.,López, Beatriz
, p. 5515 - 5522 (2007/10/03)
Treatment of 5-vinylpyranosides with Et2Zn and catalytic Pd(0), in the presence of ZnCl2, results in the formation of 5-membered carbocyclic products. This carbohydrate ring-contraction features an intramolecular allylation of a ring-opened carbohydrate aldehyde by an in situ-generated nucleophilic allylzinc species. The stereoselectivity about vinyl and free hydroxyl groups at the newly created stereogenic centers varies from low to moderate while both its extent and sense are found to depend on particular structural features (e.g. the configuration of the starting carbohydrate).
Synthesis of the JKLM-ring fragment of ciguatoxin
Baba, Takayuki,Huang, Guobin,Isobe, Minoru
, p. 6851 - 6872 (2007/10/03)
A stereoselective synthesis of the LM-ring fragment has been achieved starting from a sugar derivative. A stereoselective synthesis of the JKLM-ring fragment has been achieved through a coupling between two segments via heteroconjugate addition, seven-membered ether ring formation mediated by an acetylene cobalt complex, and spiroketalization reaction.
A new procedure for the preparation of β-keto-δ-lactones from sugars and their transformation into glycosyl acceptors in disaccharides synthesis
Bartolozzi, Alessandra,Capozzi, Giuseppe,Menichetti, Stefano,Nativi, Cristina
, p. 251 - 253 (2007/10/03)
(matrix presented) Glycals are effective starting materials for the synthesis of enantiopure β-ketone-δ-lactones. They are easily transformed, through a two-step, one-pot reaction, into the corresponding α,α′-dioxothiones which in turn can be quantitative
Application of glycals to the synthesis of oligosaccharides: Convergent total syntheses of the Lewis X trisaccharide sialyl Lewis X antigenic determinant and higher congeners
Danishefsky, Samuel J.,Gervay, Jacquelyn,Peterson, John M.,McDonald, Frank E.,Koseki, Koshi,Griffith, David A.,Oriyama, Takeshi,Marsden, Stephen P.
, p. 1940 - 1953 (2007/10/02)
Exploiting the differences in reactivity of the hydroxyl groups of glucal allows for rapid access to the sLex tetrasaccharide glycal. This compound is readily converted to the title compounds by azaglycosylation followed by deprotection. The us
Oxidation of Fully Protected Glycals by Hypervalent Iodine Reagents
Kirschning, Andreas
, p. 1228 - 1232 (2007/10/02)
A new application of organoiodine(III) is presented.Fully protected glycals are directly converted into 2,3-dihydro-4H-pyran-4-ones by benzene (PhI(OH)OTs, 1).The detailed study reveals that this conversion is independent of the rel
