1-O-Acetyl-2,3:5,6-di-O-isopropylidene-1-(2-thiazolyl)-α-D-mannofuranose | 160584-08-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: 1-O-Acetyl-2,3:5,6-di-O-isopropylidene-1-(2-thiazolyl)-α-D-mannofuranose
• 英文别名: [(3aS,4S,6R,6aS)-6-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-4-(1,3-thiazol-2-yl)-6,6a-dihydro-3aH-furo[3,4-d][1,3]dioxol-4-yl] acetate
• CAS: 160584-08-7
• 化学式: C₁₇H₂₃NO₇S
• 分子量: 385.438
• InChiKey: RRMRLXMZLWQHJG-YWAHFTAISA-N

物化性质

• 沸点：
  462.4±45.0 °C(predicted)
• 密度：
  1.36±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  26
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.76
• 拓扑面积：
  114
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  1-O-Acetyl-2,3:5,6-di-O-isopropylidene-1-(2-thiazolyl)-α-D-mannofuranose 在 三乙基硅烷 、 三氟甲磺酸三甲基硅酯 、 4 A molecular sieve 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以92%的产率得到2-(2,3:5,6-Di-O-isopropylidene-β-D-mannofuranosyl)thiazole
  参考文献：
  名称：

  Thiazole-Based Synthesis of Formyl C-Glycosides

  摘要：

  A method for the installation of the formyl group at the anomeric position of pyranoses and furanoses starting from the corresponding lactones has been developed. The strategy involves the addition of 2-lithiothiazole to the sugar lactone, followed by the silane reduction of the acetylated resultant ketol and the unmasking of the formyl group from the thiazole ring. All steps have been studied in some details to improve chemical efficiency and stereochemical control. Hence, reversed alpha:beta ratios of ketols were found in kinetic and thermodynamic mixtures, the former being consistent with a steric effect control of the substituents and the latter by the electronic effect of the ring oxygen. Seven sugar aldehydes with different D-pyranosidic (2,3,4,6-tetra-O-benzyl-gluco, -galacto, and -manno, 2-azido-3,4,6-tri-O-benzyl-2-deoxy-galacto) and D-furanosidic moieties (5-O-benzyl-2,3-isopropylidene-ribo; 2,3,5-tri-O-benzyl-ribo; 2,3:5,6-di-O-isopropylidene-manno) were prepared in 52-65% isolated overall yield from the corresponding lactone.

  DOI：

  10.1021/jo00100a050
• 作为产物：
  描述：

  2,3:5,6-二-O-异亚丙基-D-甘露糖酸-1,4-内酯 在 正丁基锂 、 三乙胺 作用下， 以 乙醚 、 正己烷 、 二氯甲烷 为溶剂， 反应 1.17h， 生成 1-O-Acetyl-2,3:5,6-di-O-isopropylidene-1-(2-thiazolyl)-α-D-mannofuranose
  参考文献：
  名称：

  Thiazole-Based Synthesis of Formyl C-Glycosides

  摘要：

  A method for the installation of the formyl group at the anomeric position of pyranoses and furanoses starting from the corresponding lactones has been developed. The strategy involves the addition of 2-lithiothiazole to the sugar lactone, followed by the silane reduction of the acetylated resultant ketol and the unmasking of the formyl group from the thiazole ring. All steps have been studied in some details to improve chemical efficiency and stereochemical control. Hence, reversed alpha:beta ratios of ketols were found in kinetic and thermodynamic mixtures, the former being consistent with a steric effect control of the substituents and the latter by the electronic effect of the ring oxygen. Seven sugar aldehydes with different D-pyranosidic (2,3,4,6-tetra-O-benzyl-gluco, -galacto, and -manno, 2-azido-3,4,6-tri-O-benzyl-2-deoxy-galacto) and D-furanosidic moieties (5-O-benzyl-2,3-isopropylidene-ribo; 2,3,5-tri-O-benzyl-ribo; 2,3:5,6-di-O-isopropylidene-manno) were prepared in 52-65% isolated overall yield from the corresponding lactone.

  DOI：

  10.1021/jo00100a050

文献信息

• Selectivity in the SmI2-induced deoxygenation of thiazolylketoses for formyl C-glycoside synthesis and revised structure of C-ribofuranosides
  作者：Alessandro Dondoni、Paolo Formaglio、Alberto Marra、Alessandro Massi

  DOI：10.1016/s0040-4020(01)00736-0

  日期：2001.9

  Deoxygenation of thiazolylketose acetates using SmI2–(CH2OH)2 or TMSOTf–Et3SiH affords thiazolyl C-glycosides with opposite α/β ratios. Examination of the thiazolyl α- and β-C-ribofuranoside pair by NOE experiments reveals that the earlier configuration assigned to one of these isomers has to be revised. Having prepared authentic anomeric α- and β-ribofuranose aldehydes from the corresponding thiazolyl

  使用SmI 2-（CH 2 OH）2或TMSOTf-Et 3 SiH对乙酸噻唑基酮糖乙酸进行脱氧，得到具有相反α/β比的噻唑基C-糖苷。通过NOE实验对噻唑基α-和β- C-核呋喃糖苷对的研究表明，必须修改分配给这些异构体之一的早期构型。已经制备正品异头α-和β-D-呋喃核糖醛从相应的噻唑基C ^由噻唑环的裂解-glycosides，各醛转化到（1→6） - c ^通过Wittig烯化-disaccharides与半乳糖6-正膦。
• Thiazolylketol acetates as glycosyl donors. Stereoselective synthesis of α-linked ketodisaccharides
  作者：Alessandro Dondoni、Alberto Marra、Isabel Rojo、Marie-Christine Scherrmann

  DOI：10.1016/0040-4020(95)01095-5

  日期：1996.2

  TMSOTf-promoted glycosidation of acetate (α)-2 and acetate 7 donors with 1 equiv of primary 3 and secondary 5 sugar alcohols acceptors gave exclusively the corresponding α-d-ketodisaccharides 4a, 8a, 11a, and 12a in 60–73% yield. On the other hand glycosidation of the acetate 6 with the primary alcohol 3 under the above conditions afforded a mixture of α- and β-d-ketodisaccharides 9a and 10a in ca

  TMSOTf促进的乙酸盐（α）-2和乙酸盐7供体与1当量的伯3和仲5糖醇受体的糖基化，以60-73％的收率仅产生相应的α-d-酮二糖4a，8a，11a和12a。另一方面，在上述条件下，乙酸6与伯醇3的糖基化得到α-和β-d-酮二糖9a和10a的混合物。在约。1：1的比例。通过与带有甲基，羧甲基和2-呋喃基的酮糖进行比较，指出了噻唑环对于这些酮醇乙酸酯的容易糖基化的重要作用。将噻唑基至甲酰基的解封反应序列应用于噻唑基酮二糖，得到相应的醛，其分别通过还原和氧化转化为醇和酯。
• Synthesis of ketosyl and ulosonyl phosphonates by Arbuzov-type glycosidation of thiazolylketol acetates
  作者：Alessandro Dondoni、Sophie Daninos、Alberto Marra、Paolo Formaglio

  DOI：10.1016/s0040-4020(98)00539-0

  日期：1998.8

  phosphonate and a hydroxymethyl (ketosyl derivatives) or carboxymethyl group (ulosonyl derivatives) at the anomeric carbon have been prepared. The synthetic route involves the trimethylsilyl triflate promoted Arbuzov-type coupling between thiazolylketol acetates and triethylphosphite to give thiazolylglycosyl phosphonates in good yields (78–93%). This glycosidation reaction was highly stereoselective giving

  在异头碳上带有二乙基膦酸酯和羟甲基（酮基衍生物）或羧甲基基团（磺酰基衍生物）的两类新型糖基膦酸酯（半乳糖，2-叠氮基-2-脱氧半乳糖，葡萄糖，甘露糖）的一些成员已经被发现。准备好了。合成途径涉及三氟甲磺酸三甲基甲硅烷基酯促进噻唑基酮醇乙酸酯和亚磷酸三乙酯之间的Arbuzov型偶联，从而以高收率（78-93％）得到噻唑基糖基膦酸酯。该糖苷化反应是高度立体选择性的，除了与葡萄糖的反应外，产生α-d-糖基膦酸酯为单一产物。衍生出几乎等量的α-和β-d-异头物的衍生物。通过噻唑至甲酰基的去封闭方案（N-烷基化，还原，水解）将膦酰基糖苷转化为醛，其分别通过甲酰基的还原或氧化而作为酮基和磺酰基二乙基膦酸酯的常见中间体。通过氢-磷偶合常数值和HETNOE实验的NMR分析，确定了所有新化合物在异头碳原子上的构型。以半乳糖吡喃糖基衍生物为例，证明了获得游离酮基和磺酰膦酸的可行性。
• A General Synthetic Route to Anomeric .alpha.-Azido and .alpha.-Amino Acids and Formal Synthesis of (+)-Hidantocidin
  作者：Alessandro Dondoni、Marie-Christine Scherrmann、Alberto Marra、Jean-Louis Delepine

  DOI：10.1021/jo00103a057

  日期：1994.12