Benzyl 3,4-O-isopropylidene-α-D-galactopyranoside | 182622-28-2

• 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: Benzyl 3,4-O-isopropylidene-α-D-galactopyranoside
• 英文别名: (3aS,4R,6S,7R,7aR)-4-(hydroxymethyl)-2,2-dimethyl-6-phenylmethoxy-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-7-ol
• CAS: 182622-28-2
• 化学式: C₁₆H₂₂O₆
• 分子量: 310.347
• InChiKey: CGYATHUHNJVXFV-QMIVOQANSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  77.4
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  Benzyl 3,4-O-isopropylidene-α-D-galactopyranoside 在 palladium dihydroxide 吡啶 、 咪唑 、 sodium hydroxide 、 氢气 、 potassium carbonate 、 溶剂黄146 、 三甲氧基磷 作用下， 以 乙腈 为溶剂， 生成 ((2S,5R,6S)-6-Benzyloxy-5-methoxy-tetrahydro-pyran-2-ylmethoxy)-tert-butyl-diphenyl-silane
  参考文献：
  名称：

  通过分子内氢提取从碳水化合物合成双螺缩醛

  摘要：

  描述了由d-吡喃半乳糖合成1,6,8-三恶二螺[4.1.5.3]十五烷15和16。关键步骤是由烷氧基促进的两个分子内氢提取反应。

  DOI：

  10.1016/0040-4039(96)01265-8
• 作为产物：
  描述：

  苄基alpha-D-吡喃半乳糖苷 、 2,2-二甲氧基丙烷 在 对甲苯磺酸 作用下， 以 丙酮 为溶剂， 反应 5.0h， 以85%的产率得到Benzyl 3,4-O-isopropylidene-α-D-galactopyranoside
  参考文献：
  名称：

  Synthesis of clustered xenotransplantation antagonists using palladium-catalyzed cross-coupling of prop-2-ynyl α-D-galactopyranoside

  摘要：

  猪肝移植的超急性排斥反应可以通过高亲和力的抗α-半乳糖苷表位（Galα1-3Galβ，Galili抗原）进行拮抗。为此，采用钯交叉偶联反应合成了含有Galili抗原的簇。因此，使用全苄化的噻苯基β-D-半乳糖呋喃糖供体5和苄基2,6-二O-苯甲酰-α-D-半乳糖呋喃糖受体3制备了苄基3-(O-α-D-半乳糖呋喃糖基)-β-D-半乳糖呋喃糖苷衍生物6。通过氢解、过乙酰化、区域选择性的α位去乙酰化、三氯乙酰亚胺活化，最后与丙炔醇在三氟醋酸的存在下偶联，成功实现了苄基到丙-2-炔基二糖8的甾醇交换。所得的丙-2-炔基二糖8以高产率（>85%）转化为通过氧化自偶联获得的二聚体10、三聚体12和四聚体17，分别利用钯催化的芳基碘交叉偶联（12, 17）。在转酯化条件下去除酯保护基团，得到完全去保护的α-Gal簇。

  DOI：

  10.1039/b101234g

文献信息

• Synthesis of dispiroacetals from carbohydrates by intramolecular hydrogen abstractions
  作者：Rosa L. Dorta、Angeles Martín、JoséA. Salazar、Ernesto Suárez、Thierry Prangé

  DOI：10.1016/0040-4039(96)01265-8

  日期：1996.8

  The synthesis of 1,6,8-trioxadispiro[4.1.5.3]pentadecanes 15 and 16 from d-galactopyranose is described. The key steps are two intramolecular hydrogen abstraction reactions promoted by alkoxy radicals.

  描述了由d-吡喃半乳糖合成1,6,8-三恶二螺[4.1.5.3]十五烷15和16。关键步骤是由烷氧基促进的两个分子内氢提取反应。
• Synthesis of clustered xenotransplantation antagonists using palladium-catalyzed cross-coupling of prop-2-ynyl α-D-galactopyranoside
  作者：Bingcan Liu、René Roy

  DOI：10.1039/b101234g

  日期：——

  Hyperacute rejection of pig liver transplantation can be antagonized using high affinity anti α-galactoside epitopes (Galα1-3Galβ, Galili antigen). To this end, clusters containing the Galili antigen were synthesized using palladium cross-coupling reactions. Thus, benzyl 3-(O-α-D-galactopyranosyl)-β-D-galactopyranoside derivative 6 was prepared using perbenzylated thiophenyl β-D-galactopyranosyl donor 5 and benzyl 2,6-di-O-benzoyl-α-D-galactopyranosyl acceptor 3. Aglycone interchange from benzyl to prop-2-ynyl disaccharide 8 was successively achieved by hydrogenolysis, peracetylation, regioselective anomeric de-O-acetylation, trichloroacetimidate activation, and finally coupling to propargyl alcohol with triflic acid. The resulting prop-2-ynyl disaccharide 8 was transformed in high yields (>85%) into dimer 10, trimer 12, and tetramer 17 using oxidative homocoupling (10) and palladium-catalyzed aryl iodide cross-coupling (12, 17), respectively. Ester protecting group removal under transesterification conditions afforded fully deprotected α-Gal clusters.

  猪肝移植的超急性排斥反应可以通过高亲和力的抗α-半乳糖苷表位（Galα1-3Galβ，Galili抗原）进行拮抗。为此，采用钯交叉偶联反应合成了含有Galili抗原的簇。因此，使用全苄化的噻苯基β-D-半乳糖呋喃糖供体5和苄基2,6-二O-苯甲酰-α-D-半乳糖呋喃糖受体3制备了苄基3-(O-α-D-半乳糖呋喃糖基)-β-D-半乳糖呋喃糖苷衍生物6。通过氢解、过乙酰化、区域选择性的α位去乙酰化、三氯乙酰亚胺活化，最后与丙炔醇在三氟醋酸的存在下偶联，成功实现了苄基到丙-2-炔基二糖8的甾醇交换。所得的丙-2-炔基二糖8以高产率（>85%）转化为通过氧化自偶联获得的二聚体10、三聚体12和四聚体17，分别利用钯催化的芳基碘交叉偶联（12, 17）。在转酯化条件下去除酯保护基团，得到完全去保护的α-Gal簇。
• Syntheses of Chiral Dispiroacetals from Carbohydrates
  作者：Rosa L. Dorta、Angeles Martín、José A. Salazar、Ernesto Suárez、Thierry Prangé

  DOI：10.1021/jo972023a

  日期：1998.4.1

  The syntheses of trioxadispiroacetals from carbohydrates are described. (5R,7S,13R)-13-Methoxy-1,6,8-trioxadispiro[4.1.5.3]pentadecane (23) and (5S,7S,13R)-13-methoxy-1,6,8-trioxadispiro[4.1.5.3]pentadecane (24) were prepared starting from D-galactose. The construction of the lateral tetrahydrofuran and tetrahydropyran rings was realized by homologation at C-1 and C-6 by appropriate tethers possessing a terminal primary alcohol. The cyclization of these alcohols at C-1 and C-5, respectively, was performed with (diacetoxyiodo)benzene and iodine in order to generate the alkoxy radicals which undergo an intramolecular hydrogen abstraction reaction. The diastereoisomers (5R,7S,13S)-13-methoxy-1,6,8-trioxadispiro[4.1.5.3]pentadecane (37) and (5S,7S,13S)-13-methoxy-1,6,8-trioxadispiro[4.1.5.3]pentadecane (38) were prepared starting from tri-O-acetyl-D-glucal using a suitable methodology in which homologation and intramolecular hydrogen abstraction were again the key steps. We believe that this protocol could be easily extended to other tricyclic dispiroacetal ring systems.