2-(trimethylsilyl)ethyl 2,3-di-O-benzoyl-β-D-galactopyranoside | 176095-70-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-(trimethylsilyl)ethyl 2,3-di-O-benzoyl-β-D-galactopyranoside
• 英文别名: Bz(-2)[Bz(-3)]Gal(b)-O-EtTMS；[(2R,3S,4S,5R,6R)-5-benzoyloxy-3-hydroxy-2-(hydroxymethyl)-6-(2-trimethylsilylethoxy)oxan-4-yl] benzoate
• CAS: 176095-70-8
• 化学式: C₂₅H₃₂O₈Si
• 分子量: 488.61
• InChiKey: UFRKJGIKQXGHNO-OAKYZLIPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.87
• 重原子数：
  34
• 可旋转键数：
  11
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  112
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  2-(trimethylsilyl)ethyl 2,3-di-O-benzoyl-β-D-galactopyranoside 在 哌啶 、 吡啶 、 四溴化碳 、 caesium carbonate 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 N,N-二异丙基乙胺 、 三苯基膦 、 甲基肼 、 三氟乙酸 作用下， 以 吡啶 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 64.84h， 生成 (4-O-acetyl-2,3-di-O-benzoyl-6-deoxy-6-methylseleno-β-D-galactopyranosyl)-(1→4)-6-O-acetyl-2,3-di-O-benzoyl-D-glucopyranose
  参考文献：
  名称：

  Expanded potential of seleno-carbohydrates as a molecular tool for X-ray structural determination of a carbohydrate–protein complex with single/multi-wavelength anomalous dispersion phasing

  摘要：

  Seleno-lactoses have been successfully synthesized as candidates for mimicking carbohydrate ligands for human galectin-9 N-terminal carbohydrate recognition domain (NCRD). Selenium was introduced into the mono-or di-saccharides using p-methylselenobenzoic anhydride (Tol(2)Se) as a novel selenating reagent. The TolSe-substituted monosaccharides were converted into selenoglycosyl donors or acceptors, which were reacted with coupling partners to afford seleno-lactoses. The seleno-lactoses were converted to the target compounds. The structure of human galectin-9 NCRD co-crystallized with 6-MeSe-lactose was determined with single/multi-wavelength anomalous dispersion (SAD/MAD) phasing and was similar to that of the co-crystal with natural lactose. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2014.02.023
• 作为产物：
  描述：

  2-(三甲基硅烷基)乙基beta-吡喃半乳糖苷 在 对甲苯磺酸 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 吡啶 、 水 、 乙腈 为溶剂， 反应 22.0h， 生成 2-(trimethylsilyl)ethyl 2,3-di-O-benzoyl-β-D-galactopyranoside
  参考文献：
  名称：

  DDQ-Mediated Oxidation of 4,6-O-Methoxybenzylidene-Protected Saccharides in the Presence of Various Nucleophiles:  Formation of 4-OH, 6-Cl, and 6-Br Derivatives

  摘要：

  Treatment of 4,6-O-p-methoxybenzylidene-protected pyranosidic mono- and disaccharides with 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), in the presence of a few equivalents of water, gave the corresponding 6- and 4-O-p-methoxybenzoates with unprotected hydroxyl groups in the 4- and 6-position in the ratio similar to 4:1 and in 85-98% yield. Dry conditions in the presence of halide salts gave the 6-deoxychloro and -bromo 4-O-p-methoxybenzoates exclusively, in >90% yield.

  DOI：

  10.1021/jo952177v

文献信息

• Silylene/Oxazolidinone Double-Locked Sialic Acid Building Blocks for Efficient Sialylation Reactions in Dichloromethane
  作者：Shinya Hanashima、Ken-ichi Sato、Yukishige Ito、Yoshiki Yamaguchi

  DOI：10.1002/ejoc.200900543

  日期：2009.9

  We describe efficient sialylation reactions in CH2Cl2 with the use of silylene/oxazolidinone double-locked sialic acid building blocks. The building blocks were synthesized from 4,5-oxazolidinone-protected phenylthiosialoside. In sialylation reactions towards primary and relatively reactive secondary hydroxy groups on the galactosides, the double-locked building blocks provided desired coupling products

  我们描述了使用亚甲硅烷基/恶唑烷酮双锁唾液酸构建块在 CH2Cl2 中的有效唾液酸化反应。构建块由 4,5-恶唑烷酮保护的苯基硫代唾液酸合成。在针对半乳糖苷上的伯羟基和相对反应性仲羟基的唾液酸化反应中，双锁结构单元以良好的收率和优异的α-选择性提供了所需的偶联产物。在与半乳糖苷的 C3-OH 的唾液酸化反应中，与使用恶唑烷酮锁定结构单元获得的结果相比，双锁定结构单元表现出明显更好的 α 选择性。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
• A 1,2-<i>trans</i> -Selective Glycosyl Donor Bearing Cyclic Protection at the C-2 and C-3 Hydroxy Groups
  作者：Nahoko Yagami、Hideki Tamai、Taro Udagawa、Akiharu Ueki、Miku Konishi、Akihiro Imamura、Hideharu Ishida、Makoto Kiso、Hiromune Ando

  DOI：10.1002/ejoc.201700671

  日期：2017.9.1

  A new 1,2-trans-selective glycosylation reaction is described. Glucosyl donors protected cyclically at the C-2 and C-3 hydroxy groups as six- (butane diacetal), seven- (tetraisopropyldisiloxanylidene), or eight- (2,3-o-xylylene) membered fused rings were synthesized in a straightforward manner. The glycosylation reactions of the glucosyl donors with various acceptors mainly generated β-glycosides under

  描述了一种新的 1,2-反式选择性糖基化反应。葡萄糖基供体在 C-2 和 C-3 羟基上被循环保护为六（丁烷二缩醛）、七（四异丙基二亚硅氧烷）或八（2,3-o-亚二甲苯基）元稠环，以直接方式合成. 在常规反应条件下，葡萄糖基供体与各种受体的糖基化反应主要生成β-糖苷。结果表明，从立体选择性和化学稳定性的角度来看，邻二甲苯基是合适的1,2-反式导向基团。通过核磁共振光谱和计算模拟对邻二甲苯保护的葡萄糖衍生物的氧代碳鎓离子进行了构象研究。结果表明氧碳鎓离子主要采用 4H3 构象，这是由于 C-2 和 C-3 处的刚性互稠环，而非环状保护的衍生物可能在构象之间波动。这些结果表明，C-2 处的伪赤道木氧基与传入的亲核试剂之间的相互作用阻碍了 1,2-顺式攻击。
• Thioester-assisted α-sialylation reaction
  作者：Shinya Hanashima、Shoji Akai、Ken-ichi Sato

  DOI：10.1016/j.tetlet.2008.05.154

  日期：2008.8

  α-Selective sialylation reactions were carried out using novel sialic acid building blocks that possess a thioester auxiliary. In contrast to other arylthio- and benzylthioester derivatives, sialyl phosphite 1a (with the phenylthioester moiety) was employed as the α-selective building block, and was reacted with various primary alcohols, including the C6–OH group of galactose and glucose, with moderate

  使用具有硫酯助剂的新型唾液酸结构单元进行α-选择性唾液酸化反应。与其他芳基硫代和苄基硫代酯衍生物相比，亚磷酸唾液酸基酯1a（具有苯基硫代酯部分）被用作α-选择性结构单元，并与各种伯醇（包括半乳糖和葡萄糖的C6-OH基团）反应，具有出色的α选择性。对于半乳糖的C3-OH，4，6-二-O-苄基半乳糖具有所需的α-键，且选择性极好。
• Synthesis of some amino and carboxy analogs of galabiose; evaluation as inhibitors of the pilus protein PapGJ96 from Escherichia coli
  作者：Henrik C. Hansen、Göran Magnusson

  DOI：10.1016/s0008-6215(98)00020-2

  日期：1998.2

  The 2'-amino-2'-deoxy, 6-amino-6-deoxy, and 6-carboxy analogs of the reference inhibitor 2-(trimethylsilyl)ethyl (alpha-D-galactopyranosyl)-(1-->4)-beta-D-galactopyranoside were synthesized and evaluated as inhibitors of the binding of the Escherichia coli-derived pilus protein PapG(J96), using an ELISA assay. The inhibitory efficiencies (K-rel; relative to the reference inhibitor) were: 157, 13, and < 8, respectively. The results support the previously proposed combining site model, where the protein carries a negatively charged amino acid residue near HO-2' and HO-6 of the galabioside. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Sialylation using N-glycolylneuraminyl phosphite donors to synthesize Neu5Gc-containing glycans
  作者：Shinya Hanashima、Taku Tomiya、Daichi Ishikawa、Shoji Akai、Ken-ichi Sato

  DOI：10.1016/j.carres.2009.03.004

  日期：2009.5

  Efficient sialylations using N-glycolylneuraminic acid (Neu5Gc) phosphite donors having an acetyl or benzyl group on the glycolyl moiety are described in the synthesis of Neu5Gc-containing glycans. Both phosphite donors 1 and 2 were readily coupled with primary and secondary acceptor alcohols in propionitrile at -78 degrees C to provide the desired glycosides with good alpha-selectivities. (C) 2009 Elsevier Ltd. All rights reserved.