methyl 2,3-di-O-acetyl-6-O-benzyl-4-thio-α-D-glucopyranoside | 262301-23-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: methyl 2,3-di-O-acetyl-6-O-benzyl-4-thio-α-D-glucopyranoside
• 英文别名: methyl 2,3-di-O-acetyl-4-thio-6-O-benzyl-α-D-glucopyranoside；[(2S,3R,4R,5R,6R)-3-acetyloxy-2-methoxy-6-(phenylmethoxymethyl)-5-sulfanyloxan-4-yl] acetate
• CAS: 262301-23-5
• 化学式: C₁₈H₂₄O₇S
• 分子量: 384.45
• InChiKey: RHWPFRYYTHCYPO-ZKXLYKBJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  26
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  81.3
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  methyl 2,3-di-O-acetyl-6-O-benzyl-4-thio-α-D-glucopyranoside 在 2,6-二叔丁基-4-甲基吡啶 、 三氟甲磺酸酐 、 sodium methylate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 2.5h， 生成 methyl 6-O-benzyl-4-S-(2,3-di-O-benzyl-4,6-O-benzylidene-β-D-mannopyranosyl)-4-thio-α-D-glucopyranoside
  参考文献：
  名称：

  Direct Stereoselective Synthesis of β-Thiomannosides

  摘要：

  A highly diastereoselective synthesis of beta-thiomannopyranosides is described in which S-phenyl 2,3-di-0-benzyl-4,6-O-benzylidene-1-deoxy-1-thia-alpha-D-mannopyranoside S-oxide is treated with triflic anhydride and 2,6-di-tert-butyl-4-methylpyridine in CH2Cl2 at -78 degrees C leading to the formation of an intermediate alpha-mannosyl triflate. Addition of primary, secondary, or tertiary thiols then leads to the beta-thiomannosides, by an S(N)2-like displacement, in good yield and with excellent stereoselectivity. Deprotection is achieved either by Birch reduction or by Zemplen deacetylation, of the acetyl protected aglycons, followed by hydrogenolysis over Pearlman's catalyst. The assignment of configuration of the beta-thiomannopyranosides is discussed in terms of the chemical shift of the mannose H5 resonance and the (1)J(CH) of the mannose anomeric carbon.

  DOI：

  10.1021/jo9914667
• 作为产物：
  描述：

  methyl 2,3-di-O-acetyl-6-O-benzyl-α-D-galactopyranoside 在 咪唑 、 碘 、 一水合肼 、 溶剂黄146 、 三苯基膦 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 6.33h， 生成 methyl 2,3-di-O-acetyl-6-O-benzyl-4-thio-α-D-glucopyranoside
  参考文献：
  名称：

  Direct Stereoselective Synthesis of β-Thiomannosides

  摘要：

  A highly diastereoselective synthesis of beta-thiomannopyranosides is described in which S-phenyl 2,3-di-0-benzyl-4,6-O-benzylidene-1-deoxy-1-thia-alpha-D-mannopyranoside S-oxide is treated with triflic anhydride and 2,6-di-tert-butyl-4-methylpyridine in CH2Cl2 at -78 degrees C leading to the formation of an intermediate alpha-mannosyl triflate. Addition of primary, secondary, or tertiary thiols then leads to the beta-thiomannosides, by an S(N)2-like displacement, in good yield and with excellent stereoselectivity. Deprotection is achieved either by Birch reduction or by Zemplen deacetylation, of the acetyl protected aglycons, followed by hydrogenolysis over Pearlman's catalyst. The assignment of configuration of the beta-thiomannopyranosides is discussed in terms of the chemical shift of the mannose H5 resonance and the (1)J(CH) of the mannose anomeric carbon.

  DOI：

  10.1021/jo9914667

文献信息

• A high-yielding, one-pot preparation of unsymmetrical glycosyl disulfides using 1-chlorobenzotriazole as an in situ trapping/oxidizing agent
  作者：Nashia Stellenboom、Roger Hunter、Mino R. Caira、László Szilágyi

  DOI：10.1016/j.tetlet.2010.07.176

  日期：2010.10

  A high-yielding, one-pot methodology for preparing unsymmetrical glycosyl disulfides derived from sugar, alkyl/aryl or cysteine thiols is reported using 1-chlorobenzotriazole (BtCl) as the oxidant. The highlight of the method is the low temperature of coupling (−78 °C) as well as the in situ trapping of the sulfenyl intermediate, which ensures that no homodimer of R1SH (R1SSR1) is formed. The coupling

  据报道，使用1-氯苯并三唑（BtCl）作为氧化剂，制备了一种高产率的一锅法方法，用于制备衍生自糖，烷基/芳基或半胱氨酸硫醇的不对称糖基二硫化物。该方法的亮点是偶联温度低（-78°C）以及亚磺基中间体的原位捕获，可确保不形成R 1 SH（R 1 SSR 1）的均二聚体。偶联效率与糖类型，糖中的硫醇位置，糖保护基团无关，并且各种产品用于说明糖生物学中许多模型系统的快速合成途径。
• Glycosylation via mixed disulfide formation using glycosylthio-phthalimides and -succinimides as glycosylsulfenyl-transfer reagents
  作者：Tünde-Zita Illyés、Tamás Szabó、László Szilágyi

  DOI：10.1016/j.carres.2011.04.020

  日期：2011.9

  The silver salts of tetra-O-acetyl alpha- or -beta-D-glycopyranosyl thiols 1a-4a react smoothly with N-bromophthalimide and N-bromosuccinimide to furnish glycosylthio-phthalimide (1b-4b) and -succinimide (1c-3c) derivatives. Reactions of these reagents with aliphatic, aromatic, and glycosyl thiols as well as with cysteine and glutathione result in the formation of glycosylated mixed disulfides under mild conditions and in good yields. The S-glycosyl-N-acylsulfenamides described here represent novel, convenient glycosylsulfenyl-transfer reagents in effecting glycosylation of various thiols, including sugars, amino acids and peptides, through disulfide formation and can, therefore, be useful in controlled glycosylation of proteins as well. (C) 2011 Elsevier Ltd. All rights reserved.
• Synthesis of S-linked carbohydrate analogues via a Ferrier reaction
  作者：David Ellis、Sarah E. Norman、Helen M.I. Osborn

  DOI：10.1016/j.tet.2008.01.042

  日期：2008.3

  In this work, the synthetic utility of the Ferrier reaction to access S-linked disaccharides and S-linked glycoamino acids has been probed. Significantly, entry to a range of 1,4- and 1,6-S-linked disaccharides has been achieved using glycals derived from glucose and galactose, and sulfur containing coupling partners derived from methyl alpha-D-glucopyranoside. Access to S-linked glycoamino acids and glycopeptides has also been achieved using protected cysteine and homocysteine coupling partners within the Ferrier reaction. Functionalisation of the Ferrier products, for example, via dihydroxylation using OsO4 or amino acid coupling, and deprotection of the targets have also been achieved. In this way, entry to materials of interest as mimics of biologically interesting disaccharides and glycopeptides has been realised, including targets derived from rare sugars such as talopyranose and gulopyranose. (C) 2008 Elsevier Ltd. All rights reserved.