methyl 3-O-allyl-4,6-O-benzylidene-β-D-idopyranoside | 1385089-75-7

• 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-4,6-O-benzylidene-β-D-idopyranoside
• 英文别名: (2S,4aR,6R,7S,8S,8aS)-6-methoxy-2-phenyl-8-prop-2-enoxy-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-7-ol
• CAS: 1385089-75-7
• 化学式: C₁₇H₂₂O₆
• 分子量: 322.358
• InChiKey: ASPVDBYGHHICFR-LGNVQCELSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  23
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  66.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 3-O-allyl-4,6-O-benzylidene-β-D-idopyranoside 、 溴甲苯 在 sodium hydride 作用下， 以 四氢呋喃 、 mineral oil 为溶剂， 以77%的产率得到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
• 作为产物：
  描述：

  甲基-Β-D-吡喃半乳糖苷 在 吡啶 、 camphor-10-sulfonic acid 、 potassium tert-butylate 作用下， 以 1,4-二氧六环 、 N,N-二甲基甲酰胺 为溶剂， 反应 96.0h， 生成 methyl 3-O-allyl-4,6-O-benzylidene-β-D-idopyranoside
  参考文献：
  名称：

  阳离子配位参与指导邻二磺酸酯的区域选择性二转化反应的证据†

  摘要：

  已经获得直接证据来证实醇盐在sp 3-杂交磺酰基酯的S-中心的异常亲核攻击。这种不寻常的反应途径导致S-O键断裂这对于区域选择性和立体选择性转化的2,3-二-关键Ö -sulfonates 4,6-的ø -亚苄基- β- d -galactopyranosides成β- d -吡喃吡喃糖苷。另外，已经提供了强有力的证据来阐明碱抗衡阳离子在转化中的作用。据认为，阳离子通过与磺酸酯中的氧配位而影响反应速率。顺式取向的相邻环氧的存在-关系极大地增强了磺酰基酯的反应性。

  DOI：

  10.1039/c3ob27336a

文献信息

• 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.
• Evidence of cation-coordination involvement in directing the regioselective di-inversion reaction of vicinal di-sulfonate esters
  作者：Rachel Hevey、Chang-Chun Ling

  DOI：10.1039/c3ob27336a

  日期：——

  Direct evidence has been obtained to confirm the unusual nucleophilic attack of an alkoxide at the S-center of sp3-hybridized sulfonyl esters. The unusual reaction pathway leads to S–O bond scission which is crucial for the regio- and stereoselective conversion of 2,3-di-O-sulfonates of 4,6-O-benzylidene-β-D-galactopyranosides into β-D-idopyranosides. In addition, strong evidence has been provided

  已经获得直接证据来证实醇盐在sp 3-杂交磺酰基酯的S-中心的异常亲核攻击。这种不寻常的反应途径导致S-O键断裂这对于区域选择性和立体选择性转化的2,3-二-关键Ö -sulfonates 4,6-的ø -亚苄基- β- d -galactopyranosides成β- d -吡喃吡喃糖苷。另外，已经提供了强有力的证据来阐明碱抗衡阳离子在转化中的作用。据认为，阳离子通过与磺酸酯中的氧配位而影响反应速率。顺式取向的相邻环氧的存在-关系极大地增强了磺酰基酯的反应性。