1,2-anhydro-3,4-di-O-benzyl-α-D-xylopyranose | 149625-86-5

• 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: 1,2-anhydro-3,4-di-O-benzyl-α-D-xylopyranose
• 英文别名: 1,2-anhydro-3,4-di-O-benzyl-D-xylopyranose；D-xylal epoxide；(1R,4R,5S,6R)-4,5-bis(phenylmethoxy)-2,7-dioxabicyclo[4.1.0]heptane
• CAS: 149625-86-5
• 化学式: C₁₉H₂₀O₄
• 分子量: 312.365
• InChiKey: MXFTWIITFRWXRX-FCGDIQPGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  40.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,2-anhydro-3,4-di-O-benzyl-α-D-xylopyranose 在 sodium azide 、 ammonium cerium (IV) nitrate 、 水 作用下， 以 乙腈 为溶剂， 反应 0.08h， 以77%的产率得到(2R,3R,4R,5R)-2-azido-4,5-bis(benzyloxy)tetrahydro-2H-pyran-3-ol
  参考文献：
  名称：

  Ceric Ammonium Nitrate-Catalyzed Azidation of 1,2-Anhydro Sugars: Application in the Synthesis of Structurally Diverse Sugar-Derived Morpholine 1,2,3-Triazoles and 1,4-Oxazin-2-ones

  摘要：

  Azidation of 1,2-anhydro sugars with NaN3 in CH3CN by using a catalytic amount of ceric ammonium nitrate has been accomplished in a regio- and stereoselective manner. Various 1,2-anhydro sugars produced 2-hydroxy-1-azido sugars in good yields which, in turn, were converted to structurally diverse sugar-derived morpholine triazoles and sugar oxazin-2-ones. These sugar derivatives were tested against various commercially available glycosidases, and two of them were found to be active in the micromolar range.

  DOI：

  10.1021/jo200260w
• 作为产物：
  描述：

  2-O-acetyl-3,4-di-O-benzyl-β-D-xylopyranosyl fluoride 在 potassium tert-butylate 作用下， 以 various solvent(s) 为溶剂， 反应 6.0h， 以87%的产率得到1,2-anhydro-3,4-di-O-benzyl-α-D-xylopyranose
  参考文献：
  名称：

  高活性取代的2,7-二氧杂双环[4.1.0]庚烷的合成，构象和糖苷偶联反应：1,2-脱水-3,4-二-O-苄基-α-d-吡喃木糖

  摘要：

  摘要以d-木糖为原料合成了标题的1,2-脱水糖（8）。合成的关键中间体是2-O-乙酰基-3,4-二-O-苄基-β-d-吡喃吡喃糖基氟，其通过叔丁醇钾的闭环转化为晶体8。将观察到的8的邻位偶合常数与通过分子力学计算得到的结果进行比较表明，吡喃糖环的构型接近4 H 5半椅。脱水糖具有高反应活性，在没有任何路易斯酸催化剂的情况下，它与1,2：3,4-二-O-异亚丙基-α-d-吡喃半乳糖的缩合反应可进行合理的收率，并在分子筛存在下定量地给出β-连接的二糖为主要产物。缩合的立体化学结果几乎不受溶剂或反应温度变化的影响。某些路易斯酸催化剂的存在导致β：α比值降低，而当高氯酸三苯甲基酯为催化剂时，主要获得的是α-连接的二糖。

  DOI：

  10.1016/0008-6215(94)84074-1

文献信息

• Stereoelectronic Factors in the Stereoselective Epoxidation of Glycals and 4-Deoxypentenosides
  作者：Laura Alberch、Gang Cheng、Seung-Kee Seo、Xuehua Li、Fabien P. Boulineau、Alexander Wei

  DOI：10.1021/jo102382r

  日期：2011.4.15

  stereoselectivity upon epoxidation with dimethyldioxirane (DMDO). In most cases, the glycals and their corresponding 4-DP isosteres share the same facioselectivity, implying that the pyran substituents are largely responsible for the stereodirecting effect. Fully substituted dihydropyrans are subject to a “majority rule”, in which the epoxidation is directed toward the face opposite to two of the three groups. Removing

  糖醛和 4-脱氧戊烯苷 (4-DP) 是具有相似结构和反应性特征的不饱和吡喃糖苷，在与二甲基二环氧乙烷 (DMDO) 环氧化时可以表现出高度的立体选择性。在大多数情况下，糖类及其相应的 4-DP 等排体具有相同的表面选择性，这意味着吡喃取代基在很大程度上负责立体定向效应。完全取代的二氢吡喃遵循“多数规则”，其中环氧化作用指向三个基团中的两个相反的表面。去除一个取代基对环氧化结果有不同的影响，这取决于它的位置以及其余两个基团的相对立体化学。总的来说，我们观察到糖醛和 4-DP 的表面选择性的最大损失是由 C3 氧的去除引起的，紧接着是 C5/异头取代基，至少是 C4/C2 氧。基于极化 π 前沿分子轨道 (PPFMO) 理论的 DFT 计算支持氧取代基在 4-DP 表面选择性中的立体电子作用，但在糖醛的情况下不太清楚。我们得出结论，4-DP 中的异头氧有助于表面选择性的立体电子偏向，而聚糖中的
• Du, Yuguo; Kong, Fanzuo, Journal of Carbohydrate Chemistry, 1995, vol. 14, # 3, p. 341 - 352
  作者：Du, Yuguo、Kong, Fanzuo

  DOI：——

  日期：——
• Organo-zinc Promoted Diastereoselective <i>C</i>-Arylation of 1,2-Anhydrosugars from Arylboronic Acids
  作者：Madhu Babu Tatina、Anil Kumar Kusunuru、Debaraj Mukherjee

  DOI：10.1021/acs.orglett.5b02364

  日期：2015.9.18

  alpha-C-arylglycosides can be obtained through the addition of aryl zinc reagents to sugar epoxides. The required aryl zinc nudeophiles can be easily obtained from the corresponding boronic acids by B-Zn exchange and attack sugar 1,2 epoxides in a highly diastereoselective fashion to generate 1,2-cis-alpha-hexapyranosyl aryl glycosides under ligand-and base-free conditions.
• Ceric Ammonium Nitrate-Catalyzed Azidation of 1,2-Anhydro Sugars: Application in the Synthesis of Structurally Diverse Sugar-Derived Morpholine 1,2,3-Triazoles and 1,4-Oxazin-2-ones
  作者：Y. Suman Reddy、A. P. John Pal、Preeti Gupta、Alafia A. Ansari、Yashwant D. Vankar

  DOI：10.1021/jo200260w

  日期：2011.8.5

  Azidation of 1,2-anhydro sugars with NaN3 in CH3CN by using a catalytic amount of ceric ammonium nitrate has been accomplished in a regio- and stereoselective manner. Various 1,2-anhydro sugars produced 2-hydroxy-1-azido sugars in good yields which, in turn, were converted to structurally diverse sugar-derived morpholine triazoles and sugar oxazin-2-ones. These sugar derivatives were tested against various commercially available glycosidases, and two of them were found to be active in the micromolar range.
• Synthesis, conformation, and glycosidic coupling reactions of highly active substituted 2,7-dioxabicyclo[4.1.0]heptanes: 1,2-anhydro-3,4-di-O-benzyl-α-d-xylopyranose
  作者：Guangbin Yang、Fanzuo Kong、Robert R. Fraser

  DOI：10.1016/0008-6215(94)84074-1

  日期：1994.5

  8 by ring closure with potassium tert -butoxide. Comparison of the observed vicinal coupling constants for 8 with the results obtained from calculations by molecular mechanics suggested that the conformation of the pyranose ring is close to a 4 H 5 half chair. The anhydro sugar was highly reactive, its condensation with 1,2:3,4-di- O -isopropylidene-α- d -galactopyranose proceeding in reasonable yield

  摘要以d-木糖为原料合成了标题的1,2-脱水糖（8）。合成的关键中间体是2-O-乙酰基-3,4-二-O-苄基-β-d-吡喃吡喃糖基氟，其通过叔丁醇钾的闭环转化为晶体8。将观察到的8的邻位偶合常数与通过分子力学计算得到的结果进行比较表明，吡喃糖环的构型接近4 H 5半椅。脱水糖具有高反应活性，在没有任何路易斯酸催化剂的情况下，它与1,2：3,4-二-O-异亚丙基-α-d-吡喃半乳糖的缩合反应可进行合理的收率，并在分子筛存在下定量地给出β-连接的二糖为主要产物。缩合的立体化学结果几乎不受溶剂或反应温度变化的影响。某些路易斯酸催化剂的存在导致β：α比值降低，而当高氯酸三苯甲基酯为催化剂时，主要获得的是α-连接的二糖。