phenyl 6-O-benzyl-1-thio-β-D-galactopyranoside | 175977-99-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 6-O-benzyl-1-thio-β-D-galactopyranoside
• 英文别名: (2R,3R,4S,5R,6S)-2-((Benzyloxy)methyl)-6-(phenylthio)tetrahydro-2H-pyran-3,4,5-triol；(2R,3R,4S,5R,6S)-2-(phenylmethoxymethyl)-6-phenylsulfanyloxane-3,4,5-triol
• CAS: 175977-99-8
• 化学式: C₁₉H₂₂O₅S
• 分子量: 362.447
• InChiKey: WMSWWJHIVWFJLE-SPOLIRPYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  25.0
• 可旋转键数：
  6.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  79.15
• 氢给体数：
  3.0
• 氢受体数：
  6.0

安全信息

• WGK Germany：
  3

反应信息

• 作为反应物：
  描述：

  phenyl 6-O-benzyl-1-thio-β-D-galactopyranoside 在 甲磺酰溴 、 silver trifluoromethanesulfonate 、 乙二胺 作用下， 以 吡啶 、 甲醇 、 乙醇 、 水 为溶剂， 反应 26.08h， 生成 4-methoxyphenyl (2,3,4-tri-O-acetyl-6-O-benzyl-β-D-galactopyranosyl)-(1->4)-<2,3,4-tri-O-benzyl-α-L-fucopyranosyl>-(1->3)-(2-acetamido-2-deoxy-β-D-glucopyranoside)
  参考文献：
  名称：

  A High Yielding Chemical Synthesis of Sialyl Lewis x Tetrasaccharide and Lewis x Trisaccharide; Examples of Regio- and Stereodifferentiated Glycosylations

  摘要：

  Virtually complete regioselective galactosylation of the diol acceptor p-methoxyphenyl 6-O-benzyl-2-deoxy-2-tetrachlorophthalimido-beta-n-glucopyranoside (8) with the donor phenyl 2,3,4-tri-O-acetyl-6-O-benzyl-1-thio-beta-D-galactopyranoside (11) gave the lactosamine derivative 14, which was fucosylated with the donor 15 to give the Le(x) trisaccharide glycoside 2 after deprotection. Regioselective sialylation of the partially protected Le(x) trisaccharide triol 24 with the sialyl donor 25 gave, after deprotection, the SLe(x) tetrasaccharide glycoside 1. The overall yields of 2 and 1 from the monosaccharide starting materials 8, 11, 15, and 25 were 56% and 29%, respectively. In contrast to the virtually complete regio- and stereoselective galactosylation of 8, fucosylation with the benzyl-protected donor 15 gave the corresponding 1-->3- and 1-->4-linked disaccharides in a ratio of 3.6:1 (highly stereo- but not regioselective glycosylation), whereas fucosylation with acetyl-protected donor 18 gave a 2.2:1 beta/alpha-mixture of 4-O-linked disaccharides (highly regio- but not stereoselective glycosylation).

  DOI：

  10.1021/jo981203x
• 作为产物：
  描述：

  苯甲醛二甲缩醛 在 三乙基硅烷 、 sodium methylate 、 三氟乙酸 作用下， 以 甲醇 、 氯仿 为溶剂， 反应 3.0h， 生成 phenyl 6-O-benzyl-1-thio-β-D-galactopyranoside
  参考文献：
  名称：

  唾液酸化路易斯X - O -Core-1苏氨酸的聚合合成

  摘要：

  选择素是一类细胞粘附分子，在炎症的初始阶段起着至关重要的作用。P-选择蛋白糖蛋白配体-1（PSGL-1）的N末端结构域与所有选择蛋白结合，但对P-选择蛋白的亲和力最高。最近的证据表明，P-选择蛋白/ PSGL-1相互作用的阻断为许多炎症性疾病的治疗提供了可行的治疗选择。在此，我们报道了苏氨酸与唾液酸路易斯X（sLe X）的总合成，其连接到Core-1- O-六糖1上，作为PSGL-1 N末端结构域的关键聚糖。使用α-选择性唾液酸化和区域选择性[4 + 2]糖基化的会聚合成是该合成的关键特征。

  DOI：

  10.1021/acs.joc.7b03117

文献信息

• Synthesis of Lewis X - O -Core-1 threonine: A building block for O -linked Lewis X glycopeptides
  作者：Mohammed Y.R. Sardar、Venkata R. Krishnamurthy、Simon Park、Appi Reddy Mandhapati、Walter J. Wever、Dayoung Park、Richard D. Cummings、Elliot L. Chaikof

  DOI：10.1016/j.carres.2017.10.002

  日期：2017.11

  expressed on many cell surface glycoproteins and plays critical roles in innate and adaptive immune responses. However, efficient synthesis of glycopeptides bearing LeX remains a major limitation for structure-function studies of the LeX determinant. Here we report a total synthesis of a LeX pentasaccharide 1 using a regioselective 1-benzenesulfinyl piperidine/triflic anhydride promoted [3 + 2] glycosylation

  LewisX（LeX）是一种分支的三糖Galβ1→4（Fucα1→3）GlcNAc，在许多细胞表面糖蛋白上表达，在先天性和适应性免疫应答中起关键作用。然而，携带LeX的糖肽的有效合成仍然是LeX决定簇结构功能研究的主要限制。在这里我们报告了使用区域选择性的1-苯亚磺酰基哌啶/三氟甲磺酸酐促进的[3 + 2]糖基化的LeX五糖1的总合成。Fmoc-苏氨酸氨基酸的存在促进了五糖在固相肽合成中的掺入，提供了通往多种O-连接的LeX糖肽的途径。所描述的方法广泛适用于合成多种复杂的糖肽，这些糖肽包含O-连接的LeX或唾液酸化的LewisX（sLeX）。
• : A mild reagent for the regioselective reductive ring opening of benzylidene acetals in carbohydrates
  作者：Lu Jiang、Tak-Hang Chan

  DOI：10.1016/s0040-4039(97)10599-8

  日期：1998.1

  is an effective reagent to reductively cleave 4,6-O-benzylidene acetals of various hexopyranosides to the corresponding 4-O-benzyl ethers. 4,6-O-Isopropylidene acetals can be similarly cleaved. Common protecting groups are stable to the reaction conditions.

  是一种有效的试剂，用于将各种六吡喃糖苷的4,6-O-亚苄基缩醛还原为相应的4-O-苄基醚。可以类似地裂解4，6-O-异亚丙基缩醛。常见的保护基对反应条件是稳定的。
• Total synthesis of VIM-2 ganglioside isolated from human chronic myelogenous leukemia cells
  作者：Taro Ehara、Akihiko Kameyama、Yutaka Yamada、Hideharu Ishida、Makoto Kiso、Akira Hasegawa

  DOI：10.1016/0008-6215(95)00353-3

  日期：1996.2

  A total synthesis of the tumor-associated glycolipid antigen, VIM-2, is described [2]. Phenyl 2,3,4-tri-O-benzoyl-6-O-benzyl-beta-D-galactopyranosyl-(1-->4)-6-O-benzy l-2- deoxy-2-phthalimido-1-thio-beta-D-glucopyranoside (7), a key intermediate prepared by condensation of phenyl 6-O-benzyl-2-deoxy-2-phthalimido-1-thio-beta-D-glucopyranoside (6) and 2,3,4-tri-O-benzoyl-6-O-benzyl-alpha-D-galactopyranosyl

  描述了肿瘤相关糖脂抗原VIM-2的全合成[2]。苯基2,3,4-三-O-苯甲酰基-6-O-苄基-β-D-吡喃半乳糖基-（1-> 4）-6-O-苄基l-2-脱氧-2-邻苯二甲酰亚胺-1-硫代β-D-吡喃葡萄糖苷（7）是通过将苯基6-O-苄基-2-脱氧-2-邻苯二甲酰亚胺基-1-硫代β-D-吡喃葡萄糖苷（6）与2,3缩合制得的关键中间体，将4-三-O-苯甲酰基-6-O-苄基-α-D-吡喃半乳糖基溴化物（5）与甲基2,3,4-三-O-苄基-1-硫代-β-L-呋喃二糖苷（ 8）得到三糖供体9，其与2-（三甲基甲硅烷基）乙基2,4,6-三-O-苄基-β-D-吡喃半乳糖基-（1→4）-2,3偶联， 6-三-O-苄基是ta-D-吡喃葡萄糖苷（10），得到五糖11。12的区域选择性糖基化（通过11的O-去苯甲酰化获得）得到七糖13，
• Guanidine/guanidinium nitrate; a mild and selective O-deacetylation reagent that leaves the N-Troc group intact
  作者：Ulf Ellervik、Göran Magnusson

  DOI：10.1016/s0040-4039(97)00105-6

  日期：1997.3

  Treatment of O-acetyl-protected sugars with a methanolic solution of guanidine/guanidinium nitrate caused the removal of the acetyl groups (91–99% isolated yield), without affecting other protecting groups. Removal of O-benzoyl groups required a longer reaction time. Of special merit is the stability of the 2,2,2-trichloroethoxycarbonylamino (N-Troc) group under these weakly basic reaction conditions

  用甲醇胍/硝酸胍的甲醇溶液处理O-乙酰基保护的糖可除去乙酰基（分离产率为91–99％），而不会影响其他保护基。除去O-苯甲酰基需要更长的反应时间。在这些弱碱性反应条件下，2,2,2-三氯乙氧羰基氨基（N -Troc）基团的稳定性特别有价值。
• “Super Armed” Glycosyl Donors:  Conformational Arming of Thioglycosides by Silylation
  作者：Christian Marcus Pedersen、Lars Ulrik Nordstrøm、Mikael Bols

  DOI：10.1021/ja071955l

  日期：2007.7.1

  Glycosyl donors protected with bulky silyl protective groups (tert-butyldimethylsilyl, TBS), on the 2-, 3-, and 4-OH groups were found to have superior reactivity compared with benzylated thioglucosides. The enhanced reactivity is explained by the stereoelectronic effects associated with the conformational change induced by the silylation. A TBS silylated thioglucoside donor has axial OR groups, whereas a benzylated thioglucoside has equatorial OR groups, leading to much more favorable charge-dipole interactions in the transition state. This concept could be used to create "super armed" glucosyl, mannosyl, rhamnosyl, and galactosyl donors, which could cross-couple with the armed acceptors, phenyl 2,3,4-tri-O- benzyl-beta-D-thioglucoside or phenyl 2,3,6-tri-O-benzyl-beta-D-thioglucoside, to give the corresponding armed disaccharides in good to excellent yields.