2-(trimethylsilyl)ethyl O-(2,3,6-tri-O-benzyl-β-D-galactopyranosyl)-(1->4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside | 117253-26-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-(trimethylsilyl)ethyl O-(2,3,6-tri-O-benzyl-β-D-galactopyranosyl)-(1->4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside
• 英文别名: 2-(trimethylsilyl)ethyl (2,3,6-tri-O-benzyl)-β-D-galactopyranosyl)-(1->4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside；2-(trimethylsilyl)ethyl 2,3,6-tri-O-benzyl-β-D-galactopyranosyl-(1->4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside；2-(trimethylsilyl)ethyl 2,3,6-tri-O-benzyl-4-O-(2,3,6-tri-O-benzyl-β-D-galactopyranosyl)-β-D-glucopyranoside；Bn(-2)[Bn(-3)][Bn(-6)]Gal(b1-4)[Bn(-2)][Bn(-3)][Bn(-6)]Glc(b)-O-EtTMS；(2R,3S,4S,5R,6S)-6-[(2R,3R,4S,5R,6R)-4,5-bis(phenylmethoxy)-2-(phenylmethoxymethyl)-6-(2-trimethylsilylethoxy)oxan-3-yl]oxy-4,5-bis(phenylmethoxy)-2-(phenylmethoxymethyl)oxan-3-ol
• CAS: 117253-26-6
• 化学式: C₅₉H₇₀O₁₁Si
• 分子量: 983.284
• InChiKey: GGTURERSSXDCLN-IGFJTUNPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.31
• 重原子数：
  71
• 可旋转键数：
  26
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  113
• 氢给体数：
  1
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  2-(trimethylsilyl)ethyl O-(2,3,6-tri-O-benzyl-β-D-galactopyranosyl)-(1->4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside 在 palladium on activated charcoal 偶氮二异丁腈 、 氢气 、 三正丁基氢锡 作用下， 以 溶剂黄146 、 甲苯 为溶剂， 45.0 ℃ 、101.33 kPa 条件下， 反应 48.0h， 生成 2-(Trimethylsilyl)ethyl 4-O-(4-deoxy-β-D-xylo-hexopyranosyl)-β-D-glucopyranoside
  参考文献：
  名称：

  2-（三甲基甲硅烷基）乙基β-乳糖苷的单脱氧衍生物的合成

  摘要：

  通过在二糖水平上脱氧，合成2-（三甲基甲硅烷基）乙基（Me 3 SiEt）β-乳糖苷的单脱氧衍生物，用于2'-，3'-，4'-和6'-单脱氧乳糖苷。通过适当保护的单脱氧Me3SiEt葡糖苷的β-D-半乳糖基化合成2-，3-和6-脱氧衍生物。在制备2-和3-脱氧乳糖苷中，硅酸银被证明是有效的糖基化促进剂。

  DOI：

  10.1016/0008-6215(93)84028-5
• 作为产物：
  描述：

  2-(trimethylsilyl)ethyl 2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-β-D-glucopyranoside 在 盐酸 、 3 A molecular sieve 、 sodium methylate 、 sodium hydride 、 sodium cyanoborohydride 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 甲醇 、 乙腈 为溶剂， 反应 3.67h， 生成 2-(trimethylsilyl)ethyl O-(2,3,6-tri-O-benzyl-β-D-galactopyranosyl)-(1->4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside
  参考文献：
  名称：

  2-(Trimethylsilyl)ethyl glycosides. 3. Synthesis, anomeric deblocking, and transformation into 1,2-trans 1-O-acyl sugars

  摘要：

  DOI：

  10.1021/jo00259a006

文献信息

• Synthesis of the globotetraose tetrasaccharide and terminal tri- and di-saccharide fragments
  作者：Ulf Nilsson、Asim K. Ray、Göran Magnusson

  DOI：10.1016/0008-6215(94)90010-8

  日期：1994.1

  groups. Removal of the anomeric TMSEt group of the globotetraoside and of the terminal trisaccharide, using trifluoroacetic acid-dichloromethane, gave the corresponding hemiacetal sugars 8 and 3. The TMSEt glycoside of the terminal trisaccharide was converted, via the 1-acetate, into the corresponding isobutyl (4) and 3-butylsulfonyl-2-[(butylsulfonyl)methyl]propyl (5) glycosides and into the TMSEt thioglycoside

  球四糖[β-D-GalNAc-（1-> 3）-alpha-D-Gal-（1-> 4）-beta-D-Gal-的2-（三甲基甲硅烷基）乙基（TMSEt）β-糖苷（1-> 4）-D-Glc]和末端三糖，以及末端二糖的甲基α-糖苷1，是由三氟甲磺酸银促进适当保护的半乳糖苷，galabioside和globotrioside的β-糖基化合成的醇与3,4,6-三-O-乙酰基-2-脱氧-2-邻苯二甲酰亚胺基-β-D-吡喃半乳糖苷氯，然后除去保护基。用三氟乙酸-二氯甲烷除去三糖四糖苷和末端三糖的异头TMSEt基团，得到相应的半缩醛糖8和3。末端三糖的TMSEt糖苷通过1-乙酸盐转化，
• Synthetic Studies on Sialoglycoconjugates 82: First Total Synthesis of Sialyl Globopentaosyl Ceramide (V³Neu5AcGb5Cer) and its Positional Isomer (V⁶Neu5AcGb5Cer)^1,2
  作者：Hideharu Ishida、Ryuichi Miyawaki、Makoto Kiso、Akira Hasegawa

  DOI：10.1080/07328309608005436

  日期：1996.2

  Abstract The first, total synthesis of sialyl globopentaosyl ceramide (V3Neu5AcGb5Cer) and its positional isomer (V6Neu5AcGb5Cer) are described. α-Selective glycosylation of 2-(trimethylsilyl)ethyl O-(2,3,6-tri-O-benzyl-β-D-galactopyranosyl)-(1→4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside (7) with the suitably protected galactose donor, methyl 3-O-acetyl-2-O-benzyl-4,6-O-benzylidene-l-thio-β-D-galactopyranoside

  摘要首先介绍了唾液酸球型戊二糖基神经酰胺（V3Neu5AcGb5Cer）及其位置异构体（V6Neu5AcGb5Cer）的全合成。2-（三甲基甲硅烷基）乙基O-（2,3,6-三-O-苄基-β-D-吡喃半乳糖基）-（1→4）-2,3,6-三-O-苄基的α-选择性糖基化-β-D-吡喃葡萄糖苷（7）与适当保护的半乳糖供体，甲基3-O-乙酰基-2-O-苄基-4,6-O-亚苄基-1-硫代-β-D-吡喃半乳糖苷得到所需的三糖通过除去O-乙酰基，将其转化为三糖受体。用甲基3-O-乙酰基-4，6-O-亚苄基-2-脱氧-2-邻苯二甲酰亚胺基-1-硫代-β-D-吡喃半乳糖苷对该受体进行糖基化，得到了球四糖衍生物，该衍生物经以下反应转化为受体12。除去邻苯二甲酰基和O-乙酰基，然后进行N-乙酰化。
• Systematic synthesis and MAG-binding activity of novel sulfated GM1b analogues as mimics of Chol-1 (α-series) gangliosides: highly active ligands for neural siglecs
  作者：Hiromi Ito、Hideharu Ishida、Brian E Collins、Susan E Fromholt、Ronald L Schnaar、Makoto Kiso

  DOI：10.1016/s0008-6215(03)00245-3

  日期：2003.7

  Systematic synthesis and myelin-associated glycoprotein (MAG)-binding activity of novel sulfated GM1b analogues structurally related to Chol-1 (alpha-series) gangliosides, high-affinity ligands for neural siglecs, are described. The suitably protected gangliotriose derivatives, 2-(trimethylsilyl)ethyl 2-acetamido-2-deoxy-6-O-levulinoyl-beta-D-galactopyranosyl-(1-->4)-2,3,6-tri-O-benzyl-beta-D-gala

  描述了与Chol-1（α系列）神经节苷脂（神经信号的高亲和力配体）结构相关的新型硫酸化GM1b类似物的系统合成和髓鞘相关糖蛋白（MAG）结合活性。适当保护的神经节三糖衍生物2-（三甲基甲硅烷基）乙基2-乙酰氨基-2-脱氧-6-O-乙酰丙酰基-β-D-吡喃半乳糖基-（1→4）-2,3,6-tri-O-苄基-β-D-吡喃半乳糖基-（1→4）-2,3,6-三-O-苄基-β-D-吡喃葡萄糖苷和2-（三甲基甲硅烷基）乙基2-乙酰氨基-2-脱氧-6- O-乙酰丙酰基-β-D-吡喃半乳糖基-（1-> 4）-2,6-二-O-苄基-3-O-乙酰丙酰基-β-D-吡喃半乳糖基-（1-> 4）-2， 3,6-tri-O-苄基-β-D-吡喃葡萄糖苷分别用α-NeuAc-（2-> 3）-半乳糖供体糖基化，得到相应的五糖，分别为94％（仅β1,3糖苷）和90％ ％（beta1,3：beta1,4 = 2：1），分别。在
• Regio- and stereo-selective synthesis of ganglioside GM1b and some positional analogs
  作者：Hubli Prabhanjan、Akihiko Kameyama、Hideharu Ishida、Makoto Kiso、Akira Hasegawa

  DOI：10.1016/0008-6215(91)80011-b

  日期：1991.11

  Total syntheses of ganglioside GM1b (IV3NeuAcGgOse4Cer) and three of its positional analogs are described. Methyl O-(methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D- glycero-alpha-D-galacto-2-nonulopyranosylonate)- (2----3)-2,4,6-tri-O-benzoyl-1-thio-beta-D-galactopyranoside (7) and methyl O-(methyl 5- acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-alpha-D-galacto-2 -nonulopyranosylonate)-(2----6)-2

  描述了神经节苷脂GM1b（IV3NeuAcGgOse4Cer）及其三个位置类似物的总合成。O-（5-乙酰氨基-4,7,8,9-四-O-乙酰基-3,5-二甲氧基-D-甘油-α-D-半乳糖-2-壬基吡喃糖醛酸甲酯）-（2 ---- 3）-2,4,6-三-O-苯甲酰基-1-硫代-β-D-吡喃半乳糖苷（7）和甲基O-（甲基5-乙酰氨基-4,7,8,9-四-O-乙酰基-3,5-二脱氧-D-甘油-α-D-半乳糖-2-壬基吡喃磺酸盐）-（2 ---- 6）-2,4-二-O-苯甲酰基-3-O-苄基-1-硫代-β-D-吡喃半乳糖苷（8）是根据我们报道的方法制备的关键糖基供体。3,4,6-三-O-乙酰基-2-脱氧-2-邻苯二甲酰亚胺基-α-D-吡喃半乳糖基溴化物与2-（三甲基甲硅烷基）乙基O-（2,3,6-三-O-苄基- β-D-吡喃半乳糖基）-（1 ---- 4）-2,3,6-三-O-苄基-β-D-吡喃葡萄
• A HIGHLY EFFICIENT TOTAL SYNTHETIC ROUTE TO α-SERIES GANGLIOSIDES: GM1α, GD1α, AND GT1α1-2
  作者：Hiromi Ito、Hideharu Ishida、Makoto Kiso

  DOI：10.1081/car-100103959

  日期：2001.3.31

  A highly efficient total synthetic route to alpha -series gangliosides GM1 alpha, GD1 alpha and GT1 alpha is described. The suitably protected gangliotriose (GgOse3) derivatives, i.e., 2-(trimethylsilyl)ethyl (2-acetamido-2-deoxy-3-O-p-methoxybenzyl-beta -D-galactopyranosyl)-(1-->4)-(2,3,6-tri-O-benzyl-beta -D-galactopyranosyl)-(1 -->4)-2,3,6-tri-O-benzyl-beta -D-glucopyranoside (8) and the corresponding III3-levulinoyl derivative (9), were regioselectively glycosylated with the phenyl 2-thioglycoside of N-acetylneuraminic acid (Neu5Ac) promoted by N-iodosuccinimide (NIS)-trimethylsilyl trifluoromethanesulfonate (TMSOTf) or trifluoromethanesulfonic acid (TfOH) in acetonitrile, to give the desired alpha -Neu5Ac-(2-->6)-gangliotriose (III(6)Neu5AcGgOse3) derivatives as the major products (11 and 12). The p-methoxybenzyl (MPM) group in 11 or the levulinoyl group in 12 was selectively removed, and the resulting 2-(trimethylsilyl)ethyl (methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-alpha -D-galacto-2-nonulopyranosylonate)-(2-->6)-(2-acetamido-2-deoxy-beta -D-galactopyranosyl)-(1-->4)-(2,3,6-tri-O-benzyl-beta -D-galactopyranosyl)-(1-->4)-2,3,6-tri-O-benzyl-beta -D-glucopyranoside (13), a key glycosyl acceptor, was systematically glycosylated with the galactose donor (14), alpha -Neu5Ac-(2-->3)-galactuse donor (15) and alpha -Neu5Ac-(2-->8)-alpha -Neu5Ac-(2-->3)-galactose donor (20) to give the protected GM1 alpha (16, 70%), GD1 alpha (17, 80%) and GT1 alpha (21, 87%) oligosaccharides, respectively, which can be converted to the target gangliosides by the introduction of ceramide and then complete deprotection.