methyl 3-O-allyl-2-O-benzyl-4,6-O-benzylidene-β-D-idopyranoside | 1385089-83-7

• 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 3-O-allyl-2-O-benzyl-4,6-O-benzylidene-β-D-idopyranoside
• 英文别名: (2S,4aR,6R,7S,8R,8aS)-6-methoxy-2-phenyl-7-phenylmethoxy-8-prop-2-enoxy-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxine
• CAS: 1385089-83-7
• 化学式: C₂₄H₂₈O₆
• 分子量: 412.483
• InChiKey: FKGPXCORSJGLIC-HYANYTLRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  30
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  55.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 3-O-allyl-2-O-benzyl-4,6-O-benzylidene-β-D-idopyranoside 在 水 、 溶剂黄146 、 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 17.0h， 以77%的产率得到methyl 3-O-allyl-2-O-benzyl-β-D-idopyranoside
  参考文献：
  名称：

  A Scalable Approach to Obtaining Orthogonally Protected β-d-Idopyranosides

  摘要：

  A practical method to obtain orthogonally protected D-idopyranose from D-galactose has been developed, which is the first method to enable synthesis of the challenging beta-D-idopyranoside linkage. The method relies on a key double inversion at O-2 and O-3 in an easily prepared D-galactose derivative, which proceeds regio- and stereoselectively through a 2,3-anhydrotalopyranoside; reaction using a selection of alkoxides affords exclusively the 3-O-alkylidopyranoside, which can be used to generate an orthogonally protected monosaccharide. The process is scalable and requires minimal purification, so it could be used to produce building blocks to aid in the synthesis of various beta-idopyranose-containing oligosaccharide targets to further probe their biological functions.

  DOI：

  10.1021/jo300764k
• 作为产物：
  描述：

  甲基-Β-D-吡喃半乳糖苷 在 potassium tert-butylate 、 sodium hydride 、 camphor-10-sulfonic acid 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 、 mineral oil 、 苯 为溶剂， 反应 96.0h， 生成 methyl 3-O-allyl-2-O-benzyl-4,6-O-benzylidene-β-D-idopyranoside
  参考文献：
  名称：

  A Scalable Approach to Obtaining Orthogonally Protected β-d-Idopyranosides

  摘要：

  A practical method to obtain orthogonally protected D-idopyranose from D-galactose has been developed, which is the first method to enable synthesis of the challenging beta-D-idopyranoside linkage. The method relies on a key double inversion at O-2 and O-3 in an easily prepared D-galactose derivative, which proceeds regio- and stereoselectively through a 2,3-anhydrotalopyranoside; reaction using a selection of alkoxides affords exclusively the 3-O-alkylidopyranoside, which can be used to generate an orthogonally protected monosaccharide. The process is scalable and requires minimal purification, so it could be used to produce building blocks to aid in the synthesis of various beta-idopyranose-containing oligosaccharide targets to further probe their biological functions.

  DOI：

  10.1021/jo300764k

文献信息

• Studies on the 6-homologation of β-D-idopyranosides
  作者：Rachel Hevey、Chang-Chun Ling

  DOI：10.1016/j.carres.2017.04.007

  日期：2017.6

  reducing conditions, and the subsequent 6-homologation via Swern oxidation and Wittig olefination to afford a 6,7-dideoxy-β-D-ido-hept-6-enopyranoside. This olefination product was found to adopt predominantly 1C4 conformation in solution by NMR experiments, which places the vinyl group at a more sterically hindered axial position and creates difficulty in subsequent hydroborations.

  β-D-异吡喃二糖是令人感兴趣的糖，因为它们在吡喃糖基环中具有异常的构象柔韧性，以及它们的β-1,2-顺式异头构型。在这里，我们报告了我们在还原条件下对4,6-O-亚苄基保护的β-D-吡喃吡喃核苷的区域选择性开环的研究，以及随后通过Swern氧化和Wittig烯化反应进行的6-同源化，得到6,7-二脱氧-β -D-ido-hept-6-enopyranoside。通过NMR实验发现该烯烃化产物在溶液中主要采用1C4构象，该构象将乙烯基置于更受空间阻碍的轴向位置，并在随后的硼氢化反应中产生困难。
• A Scalable Approach to Obtaining Orthogonally Protected β-<scp>d</scp>-Idopyranosides
  作者：Rachel Hevey、Alizée Morland、Chang-Chun Ling

  DOI：10.1021/jo300764k

  日期：2012.8.17

  A practical method to obtain orthogonally protected D-idopyranose from D-galactose has been developed, which is the first method to enable synthesis of the challenging beta-D-idopyranoside linkage. The method relies on a key double inversion at O-2 and O-3 in an easily prepared D-galactose derivative, which proceeds regio- and stereoselectively through a 2,3-anhydrotalopyranoside; reaction using a selection of alkoxides affords exclusively the 3-O-alkylidopyranoside, which can be used to generate an orthogonally protected monosaccharide. The process is scalable and requires minimal purification, so it could be used to produce building blocks to aid in the synthesis of various beta-idopyranose-containing oligosaccharide targets to further probe their biological functions.