phenyl 4-O-acetyl-2,3-O-isopropylidene-1-thio-β-L-rhamnopyranoside | 578738-07-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 4-O-acetyl-2,3-O-isopropylidene-1-thio-β-L-rhamnopyranoside
• 英文别名: [(3aR,4R,6S,7S,7aR)-2,2,6-trimethyl-4-phenylsulfanyl-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-7-yl] acetate
• CAS: 578738-07-5
• 化学式: C₁₇H₂₂O₅S
• 分子量: 338.425
• InChiKey: YXXOPDXQLPQFCF-BVEJOUGXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  79.3
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  phenyl 4-O-acetyl-2,3-O-isopropylidene-1-thio-β-L-rhamnopyranoside 在 N-碘代丁二酰亚胺 、 三氟甲磺酸 、 MS 4 Angstroem 、 sodium methylate 、 溶剂黄146 作用下， 以 甲醇 、 氯仿 为溶剂， 反应 1.25h， 生成 allyl 4-O-β-D-galactopyranosyl-3-O-α-L-rhamnopyranosyl)-β-D-glucopyranoside
  参考文献：
  名称：

  Synthesis of Lewis X trisaccharide analogues in which glucose and rhamnose replace N-acetylglucosamine and fucose, respectively

  摘要：

  Two analogues of the Le(x) trisaccharide, alpha-L-Fucp -(1 --> 3)-[beta-D-Galp -(1 --> 4)]-D-Glcp were synthesized as allyl glycosides. In these derivatives either only the N-acetylglucosamine is replaced by glucose or both the N-acetylglucosamine and the facosyl residue are replaced by glucose and rhamnose, respectively. Our synthetic scheme used armed beta-thiophenyl fuco- and rhamnoside glycosyl donors that were prepared anomerically pure from the corresponding alpha-glycosyl bromides. The protecting groups were chosen to allow access to the fully deprotected trisaccharides without reduction of the allyl glycosidic group. These analogues will be used as soluble antigens in binding experiments with anti-Le(x) antibodies and can also be conjugated to a carrier protein and used as immunogens. In the course of this synthetic work, we also describe the use of reversed-phase HPLC to purify key protected trisaccharide intermediates prior to their deprotection. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(03)00053-3
• 作为产物：
  描述：

  1,2,3,4-tetra-O-acetyl-L-rhamnopyranose 在 对甲苯磺酸 吡啶 、 氢氧化钾 、 氢溴酸 、 sodium methylate 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 、 乙酸酐 、 丙酮 、 乙腈 为溶剂， 反应 16.0h， 生成 phenyl 4-O-acetyl-2,3-O-isopropylidene-1-thio-β-L-rhamnopyranoside
  参考文献：
  名称：

  Synthesis of Lewis X trisaccharide analogues in which glucose and rhamnose replace N-acetylglucosamine and fucose, respectively

  摘要：

  Two analogues of the Le(x) trisaccharide, alpha-L-Fucp -(1 --> 3)-[beta-D-Galp -(1 --> 4)]-D-Glcp were synthesized as allyl glycosides. In these derivatives either only the N-acetylglucosamine is replaced by glucose or both the N-acetylglucosamine and the facosyl residue are replaced by glucose and rhamnose, respectively. Our synthetic scheme used armed beta-thiophenyl fuco- and rhamnoside glycosyl donors that were prepared anomerically pure from the corresponding alpha-glycosyl bromides. The protecting groups were chosen to allow access to the fully deprotected trisaccharides without reduction of the allyl glycosidic group. These analogues will be used as soluble antigens in binding experiments with anti-Le(x) antibodies and can also be conjugated to a carrier protein and used as immunogens. In the course of this synthetic work, we also describe the use of reversed-phase HPLC to purify key protected trisaccharide intermediates prior to their deprotection. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(03)00053-3

文献信息

• Synthesis of Lewis X and three Lewis X trisaccharide analogues in which glucose and rhamnose replace N-acetylglucosamine and fucose, respectively
  作者：Ari Asnani、France-Isabelle Auzanneau

  DOI：10.1016/j.carres.2008.04.017

  日期：2008.7

  Three analogues of the Le(x) trisaccharide: alpha-L-Fucp-(1 -> 3)-[beta-D-Galp-(1 -> 4)]-D-GlcNAcp as well as the Le(x) trisaccharide itself were synthesized as methyl glycosides. In the analogues, either only the fucose residue is replaced by rhamnose or both the N-acetylglucosamine and the fucosyl residues are replaced by glucose and rhamnose, respectively. Our synthetic strategy relied on the use of lactoside and 2-azido lactoside derivatives as disaccharide acceptors, which were submitted to either fucosylation or rhamnosylation. Our results confirm that the reactivity of lactose in protection and glycosylation reactions is greatly affected by (1) the structure of the aglycone and (2) the presence of an azido substituent at C-2 of the glucose moiety. Thus, a methyl lactoside acceptor was easily glycosylated at O-3 with perbenzylated P-thiophenyl fucoside and rhamnoside to give anomerically pure alpha-fucosylated and alpha-rhamnosylated trisaccharides, respectively. In contrast, the same reactions on a 2-azido methyl lactoside acceptor led to the formation of anomeric mixtures. While the alpha- and beta-fucosylated 2-azido trisaccharides could be separated by RP-HPLC, such separation was not possible for the rharmnosylated anomers. The desired rhamnosylated trisaccharide was finally obtained anomerically pure using an isopropylidene-protected rhanmosyl donor. The deprotection sequences also showed that the presence of a 2-azido substituent at C-2 of the glucose residue conferred stability to the vicinal facosidic linkage at C-3. To test their relative affinity for anti-Le(x) Abs the Lex analogues will be used as competitive inhibitors against methyl Le(x). In addition, their conformational behavior will be studied by NMR spectroscopy and molecular modeling experiments. (C) 2008 Elsevier Ltd. All rights reserved.