methyl (phenyl 2,3,4-tri-O-benzyl-1-thio-β-D-galactopyranosid)uronate | 187031-78-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl (phenyl 2,3,4-tri-O-benzyl-1-thio-β-D-galactopyranosid)uronate
• 英文别名: methyl (2S,3R,4S,5R,6S)-3,4,5-tris(phenylmethoxy)-6-phenylsulfanyloxane-2-carboxylate
• CAS: 187031-78-3
• 化学式: C₃₄H₃₄O₆S
• 分子量: 570.706
• InChiKey: SKTIDYVTFMNJIC-XXFURDKYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  41
• 可旋转键数：
  13
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  88.5
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl (phenyl 2,3,4-tri-O-benzyl-1-thio-β-D-galactopyranosid)uronate 在 palladium dihydroxide N-碘代丁二酰亚胺 、 三氟甲磺酸 、 氢气 、 溶剂黄146 作用下， 以 乙醚 、 二氯甲烷 、 水 、 乙酸乙酯 、 异丙醇 为溶剂， -60.0~-55.0 ℃ 、1000.0 kPa 条件下， 反应 2.5h， 生成 methyl α-D-galactopyranosyluronate-(1->4)-α-D-galactopyranuronic acid
  参考文献：
  名称：

  二糖4-O-α-D-半乳糖醛糖基-D-半乳糖醛酸的两种单甲酯的合成，以及用于制备在一定序列中被乌龙酸酯化的高级低聚物的前体的合成。

  摘要：

  甲基（α-D-吡喃半乳糖醛酸）-（1-> 4）-D-吡喃半乳糖醛酸和甲基α-D-吡喃半乳糖基-尿酸-（1-> 4）-D-吡喃半乳糖醛酸通过偶联甲基（苄基2,3-二-O-苄基-β-D-吡喃半乳糖苷）尿酸酯（3）或苄基（苄基2,3-二-O-苄基-β-D-吡喃半乳糖苷）尿酸酯（4）与苄基（苯基2 ，3,4-三-O-苄基-1-硫代-β-D-吡喃半乳糖苷）尿酸和（苯基2,3,4-三-O-苄基-1-硫代-β-D-吡喃半乳糖苷）尿酸，分别使用N-碘琥珀酰亚胺和三氟甲磺酸作为促进剂，然后除去苄基。4'-OH未保护的二聚体苄基（2,3-二-O-苄基-α-D-吡喃半乳糖苷）（---> 4）-（苄基2,3-二-O-苄基-β-D -galactopyranosid）尿酸盐和（2,3-di-O-苄基-alpha-D-galactopyranosyluronate）甲基-（1-> 4）由（苯基2，3-二-O-苄基-1

  DOI：

  10.1016/s0008-6215(98)00312-7
• 作为产物：
  描述：

  tert-butyl (phenyl 2,3,4-tri-O-benzyl-1-thio-β-D-galactopyranosid)uronate 在 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 生成 methyl (phenyl 2,3,4-tri-O-benzyl-1-thio-β-D-galactopyranosid)uronate
  参考文献：
  名称：

  两个d-半乳糖醛酸酯衍生物之间的高效且高度立体选择性的α（1→4）糖基化

  摘要：

  使用苯硫代糖苷作为供体，首次以高收率实现了两个d-半乳糖醛酸酯衍生物之间的高度立体选择性α（1→4）偶联。设计该方法以制备在特定位置具有甲酯基的d-半乳糖醛酸低聚物。

  DOI：

  10.1016/s0040-4039(96)02308-8

文献信息

• Differential Reactivity of α- and β-Anomers of Glycosyl Acceptors in Glycosylations. A Remote Consequence of the <i>e</i><i>ndo</i>-Anomeric Effect?
  作者：Didier Magaud、René Dolmazon、Daniel Anker、Alain Doutheau、Yves L. Dory、Pierre Deslongchamps

  DOI：10.1021/ol006039q

  日期：2000.7.1

  onic acid esters were coupled with a 1/1 mixture of alpha and beta 2,3 di-O-protected D-galactopyranosiduronic acid esters, the beta-anomer proved to be more reactive. Data from theoretical calculations suggested that the enhanced reactivity of this anomer compared with the alpha one would be due to a stronger hydrogen bond of the C-4 OH with the ring oxygen.

  当将苯基三-O-苄基-1-硫代-β-D-吡喃半乳糖醛酸酯化合物与1/1的α和β2,3二-O-保护的D-吡喃半乳糖醛酸酯化合物混合时，证明了β-端基异构体更具反应性。来自理论计算的数据表明，与α-1相比，该端基异构体的反应性增强是由于C-4 OH与环氧的氢键更强。
• An efficient and direct esterification of uronic acids using H2SO4-SiO2 at room temperature
  作者：Varsha Tiwari、Kaliyappan Murugan、Shahulhameed Sabiah、Jeyakumar Kandasamy

  DOI：10.1016/j.tetlet.2022.153852

  日期：2022.6

  A simple and convenient method for the esterification of various monosaccharide and disaccharide uronic acids, derived from glucose, galactose and mannose, was developed with different alcohols using the eco-friendly catalyst silica-sulphuric acid (H2SO4-SiO2). The esterification reactions proceeded at room temperature under mild conditions with excellent yields. Under the standard reaction conditions

  使用环保催化剂二氧化硅-硫酸（H 2 SO 4 -SiO 2），开发了一种简便的酯化方法，用于由葡萄糖、半乳糖和甘露糖衍生的各种单糖和二糖糖醛酸与不同醇的酯化反应。酯化反应在室温下温和条件下以优异的产率进行。在标准反应条件下，对乙酰基、苯甲酰基、新戊酰基、异亚丙基、苄基、萘基等各种敏感保护基团具有良好的耐受性。部分保护的糖醛酸在不发生自缩合反应的情况下进行酯化。
• Stereodirecting Effect of the Pyranosyl C-5 Substituent in Glycosylation Reactions
  作者：Jasper Dinkelaar、Ana Rae de Jong、Robert van Meer、Mark Somers、Gerrit Lodder、Herman S. Overkleeft、Jeroen D. C. Codée、Gijsbert A. van der Marel

  DOI：10.1021/jo900662v

  日期：2009.7.17

  The stereodirecting effect of the glycosyl C-5 substituent has been investigated in a series of D-pyranosyl thioglycoside donors and related to their preferred positions in the intermediate H-3(4) and H-4(3) half-chair oxacarbenium ions. Computational studies showed that an axially positioned C-5 carboxylate ester can stabilize the (3)H4 half-chair oxacarbenium ion conformer by donating electron densit from its carbonyl function into the electron-poor oxacarbenium ion functionality. A similar stabilization can be achieved by a C-5 benzyloxyrnethyl group, but,the magnitude of this stabilization is significantly smaller than for the C-5 carboxylate ester. As a result, the preference of the C-5 benzyloxymethyl to occupy an axial position in the half-chair oxacarbenium ions is much reduced compared to the C-5 carboxylate ester. To minimize steric interactions, a C-5 methyl group prefers to adopt an equatorial position and therefore favors the H-4(3) half-chair oxacarbenium ion. When all pyranosyl substituents occupy their favored position in one of the two intermediate half-chair oxacarbenium ions, highly stereoselective glycosylations can be achieved as revealed by the excellent beta-selectivity of mannuronate esters and alpha-selectivity of 6-deoxygulosides.
• Synthesis of the two monomethyl esters of the disaccharide 4-O-α-d-galacturonosyl-d-galacturonic acid and of precursors for the preparation of higher oligomers methyl uronated in definite sequences
  作者：Didier Magaud、Cyrille Grandjean、Alain Doutheau、Daniel Anker、Vladimir Shevchik、Nicole Cotte-Pattat、Janine Robert-Baudouy

  DOI：10.1016/s0008-6215(98)00312-7

  日期：1998.12

  ate were prepared from methyl (phenyl 2,3-di-O-benzyl-1-thio-4-O-trimethylsilyl-beta-D-galactopyranosid) uronate and benzyl (phenyl 2,3-di-O-benzyl-1-thio-4-O-trimethylsilyl-beta-D-galactopyranosid) uronate and acceptors 4 or 3, respectively. These compounds have been designed to serve as precursors for the preparation of higher-membered D-galacturonic acid oligomers methyl esterified in definite positions

  甲基（α-D-吡喃半乳糖醛酸）-（1-> 4）-D-吡喃半乳糖醛酸和甲基α-D-吡喃半乳糖基-尿酸-（1-> 4）-D-吡喃半乳糖醛酸通过偶联甲基（苄基2,3-二-O-苄基-β-D-吡喃半乳糖苷）尿酸酯（3）或苄基（苄基2,3-二-O-苄基-β-D-吡喃半乳糖苷）尿酸酯（4）与苄基（苯基2 ，3,4-三-O-苄基-1-硫代-β-D-吡喃半乳糖苷）尿酸和（苯基2,3,4-三-O-苄基-1-硫代-β-D-吡喃半乳糖苷）尿酸，分别使用N-碘琥珀酰亚胺和三氟甲磺酸作为促进剂，然后除去苄基。4'-OH未保护的二聚体苄基（2,3-二-O-苄基-α-D-吡喃半乳糖苷）（---> 4）-（苄基2,3-二-O-苄基-β-D -galactopyranosid）尿酸盐和（2,3-di-O-苄基-alpha-D-galactopyranosyluronate）甲基-（1-> 4）由（苯基2，3-二-O-苄基-1
• An efficient and highly stereoselective α(1→4) glycosylation between two d-galacturonic acid ester derivatives
  作者：Didier Magaud、Cyrille Grandjean、Alain Doutheau、Daniel Anker、Vladimir Shevchik、Nicole Cotte-Pattat、Janine Robert-Baudouy

  DOI：10.1016/s0040-4039(96)02308-8

  日期：1997.1

  The highly stereoselective α(1→4) coupling between two d-galacturonic acid ester derivatives was accomplished in good yields, for the first time, using a phenylthioglycoside as donor. The method was designed to prepare d-galacturonic acid oligomers with methyl ester groups in definite positions.

  使用苯硫代糖苷作为供体，首次以高收率实现了两个d-半乳糖醛酸酯衍生物之间的高度立体选择性α（1→4）偶联。设计该方法以制备在特定位置具有甲酯基的d-半乳糖醛酸低聚物。