phenyl 1-thio-α-D-rhamnopyranoside | 1207976-08-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 1-thio-α-D-rhamnopyranoside
• 英文别名: (2R,3S,4S,5S,6R)-2-methyl-6-phenylsulfanyloxane-3,4,5-triol
• CAS: 1207976-08-6
• 化学式: C₁₂H₁₆O₄S
• 分子量: 256.323
• InChiKey: YBOVKFRFMWFKCC-AZOIZPIDSA-N

物化性质

• 沸点：
  446.6±45.0 °C(predicted)
• 密度：
  1.37±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.61
• 重原子数：
  17.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  69.92
• 氢给体数：
  3.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  phenyl 1-thio-α-D-rhamnopyranoside 、 乙酸酐 在 吡啶 作用下， 生成
  参考文献：
  名称：

  Synthesis of orthogonally protected d-olivoside, 1,3-di-O-acetyl-4-O-benzyl-2,6-dideoxy-d-arabinopyranose, as a C-glycosyl donor

  摘要：

  1,3-Di-O-acetyl-4-O-benzyl-2,6-dideoxy-D-arabinopyranose (11) was synthesised from thiophenyl alpha-D-mannopyranoside (21) in an eight-step sequence. Tosylation of 21 and subsequent reaction with 2,2-dimethoxypropane gave tosylate 22, which upon treatment with lithium aluminium hydride furnished 6-deoxy glycoside 24 and by-product thiophenyl 6-deoxy-2-O-isopropyl-alpha-D-arabinopyranoside. The X-ray crystal structure of the latter was determined. Benzylation of the 4-hydroxyl group of 24 and Subsequent protecting group manipulation gave D-rhamnosyl bromide 29, which on treatment with zinc-copper couple gave the orthogonally protected D-rhamnal 30. Triphenylphosphine hydrogen bromide catalysed addition of acetic acid to 30 furnished the target molecule 11. The scandium(III) triflate promoted reaction of 11 and 2-naphthol gave the corresponding C-glycoside 36 in 86% yield. Crown Copyright (C) 2009 Published by Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2009.03.092
• 作为产物：
  描述：

  Phenyl 2,3-O-isopropylidene-1-thio-α-D-rhamnopyranoside 在 甲醇 、 三氟乙酸 作用下， 生成 phenyl 1-thio-α-D-rhamnopyranoside
  参考文献：
  名称：

  Synthesis of orthogonally protected d-olivoside, 1,3-di-O-acetyl-4-O-benzyl-2,6-dideoxy-d-arabinopyranose, as a C-glycosyl donor

  摘要：

  1,3-Di-O-acetyl-4-O-benzyl-2,6-dideoxy-D-arabinopyranose (11) was synthesised from thiophenyl alpha-D-mannopyranoside (21) in an eight-step sequence. Tosylation of 21 and subsequent reaction with 2,2-dimethoxypropane gave tosylate 22, which upon treatment with lithium aluminium hydride furnished 6-deoxy glycoside 24 and by-product thiophenyl 6-deoxy-2-O-isopropyl-alpha-D-arabinopyranoside. The X-ray crystal structure of the latter was determined. Benzylation of the 4-hydroxyl group of 24 and Subsequent protecting group manipulation gave D-rhamnosyl bromide 29, which on treatment with zinc-copper couple gave the orthogonally protected D-rhamnal 30. Triphenylphosphine hydrogen bromide catalysed addition of acetic acid to 30 furnished the target molecule 11. The scandium(III) triflate promoted reaction of 11 and 2-naphthol gave the corresponding C-glycoside 36 in 86% yield. Crown Copyright (C) 2009 Published by Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2009.03.092

文献信息

• Site-Selective C–O Bond Editing of Unprotected Saccharides
  作者：Guanjie Wang、Chang Chin Ho、Zhixu Zhou、Yong-Jia Hao、Jie Lv、Jiamiao Jin、Zhichao Jin、Yonggui Robin Chi

  DOI：10.1021/jacs.3c10963

  日期：2024.1.10

  catalytic site-selective installation of a photoredox active carboxylic ester group to a specific hydroxyl unit of an unprotected sugar. The second step, namely, “editing”, features a C–O bond cleavage to form a carbon radical intermediate that undergoes further transformations such as C–H and C–C bond formations. Our strategy constitutes the most effective and shortest route in direct transformation and modification

  葡萄糖及其多羟基糖类似物是复杂的分子，是生物大分子、天然产物、药物和农用化学品的重要结构成分。在糖的广阔领域内，一个重要的研究领域围绕着将天然丰富的糖单元化学转化为复杂或不常见的分子，例如寡糖或稀有糖。然而，部分由于具有相似反应性的多个羟基的存在以及立体化学产生的结构复杂性，将未受保护的糖转化为所需的目标分子仍然具有挑战性。其中一项艰巨的挑战在于糖类中 C-O 键的高效、选择性激活和修饰。在这项研究中，我们公开了一种模块化的2重“标签编辑”策略，该策略允许直接和选择性地编辑糖的C-O键，从而能够快速制备有价值的分子，例如稀有糖和药物衍生物。第一步称为“标记”，涉及将光氧化还原活性羧酸酯基团催化位点选择性安装到未受保护的糖的特定羟基单元上。第二步，即“编辑”，其特征是 C-O 键断裂，形成碳自由基中间体，该中间体经历进一步的转化，例如 C-H 和 C-C 键形成。我们的策略构成了直接转化和修
• Goemez, Ana M.; Casillas, Marta; Rodriguez, Benjamin, ARKIVOC, 2010, vol. 2010, # 3, p. 288 - 302
  作者：Goemez, Ana M.、Casillas, Marta、Rodriguez, Benjamin、Valverde, Serafin、Loepez, J. Cristoebal

  DOI：——

  日期：——
• Synthesis of orthogonally protected d-olivoside, 1,3-di-O-acetyl-4-O-benzyl-2,6-dideoxy-d-arabinopyranose, as a C-glycosyl donor
  作者：Hasnah Osman、David S. Larsen、Jim Simpson

  DOI：10.1016/j.tet.2009.03.092

  日期：2009.5

  1,3-Di-O-acetyl-4-O-benzyl-2,6-dideoxy-D-arabinopyranose (11) was synthesised from thiophenyl alpha-D-mannopyranoside (21) in an eight-step sequence. Tosylation of 21 and subsequent reaction with 2,2-dimethoxypropane gave tosylate 22, which upon treatment with lithium aluminium hydride furnished 6-deoxy glycoside 24 and by-product thiophenyl 6-deoxy-2-O-isopropyl-alpha-D-arabinopyranoside. The X-ray crystal structure of the latter was determined. Benzylation of the 4-hydroxyl group of 24 and Subsequent protecting group manipulation gave D-rhamnosyl bromide 29, which on treatment with zinc-copper couple gave the orthogonally protected D-rhamnal 30. Triphenylphosphine hydrogen bromide catalysed addition of acetic acid to 30 furnished the target molecule 11. The scandium(III) triflate promoted reaction of 11 and 2-naphthol gave the corresponding C-glycoside 36 in 86% yield. Crown Copyright (C) 2009 Published by Elsevier Ltd. All rights reserved.