methyl 4,6-O-benzylidene-3-O-picolinyl-α-D-glucopyranoside

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: methyl 4,6-O-benzylidene-3-O-picolinyl-α-D-glucopyranoside
• 英文别名: [(2R,4aR,6S,7R,8R,8aR)-7-hydroxy-6-methoxy-2-phenyl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-8-yl] pyridine-2-carboxylate
• 化学式: C₂₀H₂₁NO₇
• 分子量: 387.389
• InChiKey: VUWWIVZRSXHDOB-HZLBELHRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  28
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  96.3
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  methyl 4,6-O-benzylidene-3-O-picolinyl-α-D-glucopyranoside 、 3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl phosphorochloridite 在 吡啶 作用下， 以 甲苯 为溶剂， 生成 [(2R,4aR,6S,7R,8S,8aR)-6-methoxy-2-phenyl-7-(2,4,8,10-tetratert-butylbenzo[d][1,3,2]benzodioxaphosphepin-6-yl)oxy-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-8-yl] pyridine-2-carboxylate
  参考文献：
  名称：

  吡喃糖苷亚磷酸酯-吡啶配体在对映选择性金属催化的烯丙基取代和共轭1,4-加成中的应用

  摘要：

  在金属催化的烯丙基取代和几种底物类型的共轭1，4-加成反应中已应用了一系列的吡喃葡萄糖苷亚磷酸酯-吡啶配体。我们已经能够鉴定出在环状底物的Pd催化的分子间烯丙基取代（ee高达86％）和去对称化（ee高达94％）以及铜催化的挑战性脂族烯酮的共轭加成中提供有希望的对映选择性的配体。 （ee高达90％）。

  DOI：

  10.1016/j.tetasy.2013.06.011
• 作为产物：
  描述：

  4,6-O-benzylidene-1-O-methyl-α-D-glucopyranoside 在 4-二甲氨基吡啶 、 TEA 、 zinc diacetate 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 10.0h， 生成 methyl 4,6-O-benzylidene-3-O-picolinyl-α-D-glucopyranoside
  参考文献：
  名称：

  Picolinyl group as an efficient alcohol protecting group: cleavage with Zn(OAc)2·2H2O under a neutral condition

  摘要：

  As an efficient alcohol protecting group, picolinates (Pic), prepared from the corresponding alcohols using commercial picolinoyl chloride, are readily cleaved by Zn(OAc)(2) or Cu(OAc)(2), even in the presence of other common alcohol protecting groups. Moreover, the picolinyl group at C-2 position in carbohydrates can be selectively cleaved to give methyl 4,6-O-benzylidene-3-O-picolinyl-alpha-D-glucopyranoside and 3-O-picolinyl methyl-4,6-O-benzylidene-alpha-D-galactopyranoside in good yields. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2005.05.125

文献信息

• The application of pyranoside phosphite-pyridine ligands to enantioselective Ir-catalyzed hydrogenations of highly unfunctionalized olefins
  作者：Jessica Margalef、Matteo Lega、Francesco Ruffo、Oscar Pàmies、Montserrat Diéguez

  DOI：10.1016/j.tetasy.2012.06.025

  日期：2012.7

  Eight (biaryl)phosphite/pyridine ligands 1-2a-d have been prepared by the modular functionalization of positions C-2 and C-3 of two D-glucopyranoside backbones. The chiral ligands were examined in the iridium-catalyzed asymmetric hydrogenation of poorly functionalized alkenes, as a function of the relative position of the coordinating groups and the geometric properties of the biaryl phosphite moieties. Enantiomeric excesses of up to 90% were achieved in the hydrogenation of E-2-(4-methoxyphenyl)-2-butene by using 1a and 1c, which seemingly combine the beneficial effect of the phosphite at the 2-position with the matching (R-ax)-configuration of their encumbered biaryl substituents. The results of the hydrogenation of more challenging substrates, such as Z-trisubstituted alkenes, alkenes with a neighboring polar group or demanding 1,1-di-substituted alkenes, generally confirmed this trend, and in some significant cases, the chiral hydrogenated products were isolated with ees of 65-79%. (C) 2012 Elsevier Ltd. All rights reserved.