methyl 4,6-O-benzylidene-2-deoxy-2-(1-piperidinyl)-α-D-glucopyranoside

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 4,6-O-benzylidene-2-deoxy-2-(1-piperidinyl)-α-D-glucopyranoside
• 英文别名: (2R,4aR,6S,7R,8R,8aS)-6-methoxy-2-phenyl-7-piperidin-1-yl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-8-ol
• 化学式: C₁₉H₂₇NO₅
• 分子量: 349.427
• InChiKey: OQXHTXPNKYSWCG-UPGMHYFXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  25
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  60.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  methyl 4,6-O-benzylidene-α-D-arabino-hexopyranoside-2-ulose Z-oxime 在 lithium aluminium tetrahydride 、 硫酸 、 potassium carbonate 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 40.0h， 生成 methyl 4,6-O-benzylidene-2-deoxy-2-(1-piperidinyl)-α-D-glucopyranoside
  参考文献：
  名称：

  使用碳水化合物支架在不对称催化中进行精确的结构活性关系以进行精细调节：添加二烷基锌-醛。

  摘要：

  从核心D-氨基葡萄糖支架上迅速构建24种立体化学和功能多样的碳水化合物配体结构，可以评估配体促进锌酸酯加成醛中广泛的结构活性关系，δG+ / +（RS）的变化最高可达5650 J mol（-1）会产生不对称感应的相反感觉，并且与基于几种配体X射线结构和分子力学分析的模型一致。使用关键的二面角和N-2的空间体积进行对映选择性的因子分析，也突出了在配体构建中使用因子设计的潜力。

  DOI：

  10.1039/b309715n

文献信息

• Precise structure activity relationships in asymmetric catalysis using carbohydrate scaffolds to allow ready fine tuning: dialkylzinc–aldehyde additions
  作者：Daniel P. G. Emmerson、Renaud Villard、Claudia Mugnaini、Andrei Batsanov、Judith A. K. Howard、William P. Hems、Robert P. Tooze、Benjamin G. Davis

  DOI：10.1039/b309715n

  日期：——

  carbohydrate ligand structures from a core D-glucosamine scaffold has allowed the evaluation of broad ranging structure activity relationships in ligand accelerated zincate additions to aldehydes, with variations in deltadeltaG+/+(R-S) of up to 5650 J mol(-1) that create opposing senses of asymmetric induction and that are consistent with models based on several ligand X-ray structures and molecular mechanics

  从核心D-氨基葡萄糖支架上迅速构建24种立体化学和功能多样的碳水化合物配体结构，可以评估配体促进锌酸酯加成醛中广泛的结构活性关系，δG+ / +（RS）的变化最高可达5650 J mol（-1）会产生不对称感应的相反感觉，并且与基于几种配体X射线结构和分子力学分析的模型一致。使用关键的二面角和N-2的空间体积进行对映选择性的因子分析，也突出了在配体构建中使用因子设计的潜力。
• Enantioselective Arylations Catalyzed by Carbohydrate-Based Chiral Amino Alcohols
  作者：Ana Dionéia Wouters、Gustavo H. G. Trossini、Hélio A. Stefani、Diogo S. Lüdtke

  DOI：10.1002/ejoc.201000113

  日期：2010.4

  The application of carbohydrate-derived amino alcohols in the asymmetric arylation of aldehydes by using arylboronic acids as the source of transferable aryl groups is described. The best ligand is derived from the readily available sugar D-xylose and it mediates the addition of a range of arylboronic acids to various aromatic aldehydes in excellent yields and high enantiomeric excesses.

  描述了碳水化合物衍生的氨基醇在使用芳基硼酸作为可转移芳基来源的醛的不对称芳基化中的应用。最好的配体来源于容易获得的糖 D-木糖，它介导了一系列芳基硼酸以优异的产率和高对映体过量添加到各种芳香醛中。
• Carbohydrate-derived aminoalcohol ligands for asymmetric Reformatsky reactions
  作者：Daniel P.G. Emmerson、William P. Hems、Benjamin G. Davis

  DOI：10.1016/j.tetasy.2004.11.049

  日期：2005.1

  Members of a family of functionally and stereochemically diverse D-glucosamine-derived tertiary aminoalcohol ligands have been used to promote the asymmetric Reformatsky reaction. The beta-hydroxyester product tert-butyl 3-phenyl-3-hydroxy-propanoate was obtained enriched in either the (+)-(R) (up to 74% ee) or (-)-(S) (up to 42% ee) enantiomer depending on the choice of ligand. Although the selectivities are modest in absolute terms they represent some the better selectivities obtained to date for this reaction. A H-1 NMR study was conducted to investigate this selectivity and suggested a secondary binding mode between ligand and zinc in addition to the expected N-2, O-3 coordination. (C) 2004 Elsevier Ltd. All rights reserved.