(2S,3S,4R,5R,6R)-3,4,5-Tris-benzyloxy-2-methyl-6-phenylsulfanyl-tetrahydro-pyran | 503065-79-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2S,3S,4R,5R,6R)-3,4,5-Tris-benzyloxy-2-methyl-6-phenylsulfanyl-tetrahydro-pyran
• 英文别名: 1-(Phenylthio)-2-O,3-O,4-O-tribenzyl-1-deoxy-beta-L-rhamnopyranose；(2S,3S,4R,5R,6R)-2-methyl-3,4,5-tris(phenylmethoxy)-6-phenylsulfanyloxane
• CAS: 503065-79-0
• 化学式: C₃₃H₃₄O₄S
• 分子量: 526.697
• InChiKey: WGAOZACWMVPQOY-JJFDDFPNSA-N

物化性质

• 熔点：
  103 °C
• 沸点：
  644.5±55.0 °C(Predicted)
• 密度：
  1.20±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.9
• 重原子数：
  38
• 可旋转键数：
  11
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  62.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  甲基2,3,6-三-O-苄基-ALPHA-D-吡喃葡萄糖苷 、 (2S,3S,4R,5R,6R)-3,4,5-Tris-benzyloxy-2-methyl-6-phenylsulfanyl-tetrahydro-pyran 在 辛酸铑 、 2,6-二叔丁基-4-甲基吡啶三氟甲磺酸盐 、 methyl 2-(4-chlorophenyl)-2-diazoacetate 作用下， 以 二氯甲烷 为溶剂， 以90%的产率得到methyl 2,3,6-tri-O-benzyl-4-O-(2,3,4-tri-O-benzyl-L-rhamnosyl)-α-D-glucopyranoside
  参考文献：
  名称：

  通过连续的铑 (II) 和布朗斯台德酸催化实现糖基化

  摘要：

  在此，我们报道了一种高效的糖基化反应，包括两个按时间顺序精心设计的催化循环：1）铑催化形成锍叶立德；2) Brønsted 酸催化形成锍离子。该协议强调了一种有效且稳健的策略，可从适合糖基化的糖基锍叶立德前体制备糖基锍离子。

  DOI：

  10.1021/jacs.9b04619

文献信息

• Effective One-pot Synthesis of H type 1 and 2 Trisaccharide Derivatives Using Glycal Epoxide
  作者：Hiroshi Tanaka、Nobuatsu Matoba、Takashi Takahashi

  DOI：10.1246/cl.2005.400

  日期：2005.3

  We describe an efficient synthesis of H type 1 and 2 trisaccharides by one-pot glycosylation involving glycosidation of glycal epoxide.

  我们描述了一种有效合成 H 1 型和 2 型三糖的方法，包括一锅糖基化，包括环氧化糖苷化。
• 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.
• Glycosylation Enabled by Successive Rhodium(II) and Brønsted Acid Catalysis
  作者：Lingkui Meng、Peng Wu、Jing Fang、Ying Xiao、Xiong Xiao、Guangsheng Tu、Xiang Ma、Shuang Teng、Jing Zeng、Qian Wan

  DOI：10.1021/jacs.9b04619

  日期：2019.7.31

  reaction comprises two chronological meticulously-designed catalytic cycles: 1) rhodium-catalyzed formation of sulfonium ylide; 2) Brønsted acid-catalyzed formation of sulfonium ion. This protocol highlight-ed an effective and robust tactic to prepare glycosyl sulfonium ion from glycosyl sulfonium ylide precursor amenable for glycosylation.

  在此，我们报道了一种高效的糖基化反应，包括两个按时间顺序精心设计的催化循环：1）铑催化形成锍叶立德；2) Brønsted 酸催化形成锍离子。该协议强调了一种有效且稳健的策略，可从适合糖基化的糖基锍叶立德前体制备糖基锍离子。