phenyl 4,6-di-O-benzyl-2,3-O-carbonyl-1-thio-β-D-glucopyranoside | 864966-87-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 4,6-di-O-benzyl-2,3-O-carbonyl-1-thio-β-D-glucopyranoside
• 英文别名: (3aR,4S,6R,7R,7aS)-7-phenylmethoxy-6-(phenylmethoxymethyl)-4-phenylsulfanyl-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-2-one
• CAS: 864966-87-0
• 化学式: C₂₇H₂₆O₆S
• 分子量: 478.566
• InChiKey: UYEXQKOJQBGMPW-RTJMFUJLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  34
• 可旋转键数：
  9
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  88.5
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  phenyl 4,6-di-O-benzyl-2,3-O-carbonyl-1-thio-β-D-glucopyranoside 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以23%的产率得到(3aR,4R,6R,7R,7aS)-7-(benzyloxy)-6-((benzyloxy)methyl)-4-(phenylthio)tetrahydro-4H-[1,3]dioxolo[4,5-c]pyran-2-one
  参考文献：
  名称：

  构象受限的糖精苷的环内切割的证据。

  摘要：

  与其他吡喃糖苷相比，在存在路易斯酸的情况下，携带2，3-反式氨基甲酸酯和碳酸酯的吡喃糖苷很容易从β方向向α方向异构化。该反应是由吡喃糖苷的环内切割引起的。通过分子内和分子间Friedel-Crafts反应，添加氯化物和还原生成的阳离子，获得了椅型构象受限吡喃糖苷的环内裂解证据。另一方面，构象失真的吡喃糖苷从未以内环方式被裂解。

  DOI：

  10.1002/chem.200900064
• 作为产物：
  描述：

  phenyl 2,3-di-O-(2,3-dimethoxybutane-2,3-diyl)-1-thio-β-D-glucopyranoside 在 sodium hydride 、 三乙胺 、 三氟乙酸 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 10.17h， 生成 phenyl 4,6-di-O-benzyl-2,3-O-carbonyl-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  Stereocontrolled Formation of β-Glucosides and Related Linkages in the Absence of Neighboring Group Participation:  Influence of a trans-Fused 2,3-O-Carbonate Group

  摘要：

  [GRAPHICS]Phenyl 4,6-di-O-benzyl-2,3-O-carbonyl-beta-D-glucothiopyranoside and the regiosiomeric phenyl 2,6-di-O-benzyl-3,4-O-carbonyl-beta-D-glucothiopyranoside were prepared and studied as glucosyl donors at -60 degrees C in dichloromethane with preactivation by 1-benzenesulfinyl piperidine before addition of the acceptor alcohol. The 2,3-O-carbonate protected donor showed moderate to excellent beta-selectivity under these conditions depending on the acceptor employed, thereby providing a means for 1,2-trans-equatorial glycosidic bonds without recourse to neighboring group participation and its associated problem of ortho ester formation. In contrast, the 3,4-O-carbonate protected donor showed moderate to no beta-selectivity under the conditions employed. The results obtained in this study with carbonate protected glucopyranosyl donors are contrasted with those obtained previously in the manno- and rhamnopyranosyl series when the 2,3-O-carbonate protected is (x-selective and the 3,4-O-carbonate is beta-selective.

  DOI：

  10.1021/jo0508999

文献信息

• Stereocontrolled Formation of β-Glucosides and Related Linkages in the Absence of Neighboring Group Participation:  Influence of a <i>trans</i>-Fused 2,3-<i>O</i>-Carbonate Group
  作者：David Crich、Prasanna Jayalath

  DOI：10.1021/jo0508999

  日期：2005.9.1

  [GRAPHICS]Phenyl 4,6-di-O-benzyl-2,3-O-carbonyl-beta-D-glucothiopyranoside and the regiosiomeric phenyl 2,6-di-O-benzyl-3,4-O-carbonyl-beta-D-glucothiopyranoside were prepared and studied as glucosyl donors at -60 degrees C in dichloromethane with preactivation by 1-benzenesulfinyl piperidine before addition of the acceptor alcohol. The 2,3-O-carbonate protected donor showed moderate to excellent beta-selectivity under these conditions depending on the acceptor employed, thereby providing a means for 1,2-trans-equatorial glycosidic bonds without recourse to neighboring group participation and its associated problem of ortho ester formation. In contrast, the 3,4-O-carbonate protected donor showed moderate to no beta-selectivity under the conditions employed. The results obtained in this study with carbonate protected glucopyranosyl donors are contrasted with those obtained previously in the manno- and rhamnopyranosyl series when the 2,3-O-carbonate protected is (x-selective and the 3,4-O-carbonate is beta-selective.
• Evidence for Endocyclic Cleavage of Conformationally Restricted Glycopyranosides
  作者：Shino Manabe、Kazuyuki Ishii、Daisuke Hashizume、Hiroyuki Koshino、Yukishige Ito

  DOI：10.1002/chem.200900064

  日期：2009.7.13

  reaction is caused by endocyclic cleavage of the pyranosides. Evidence for endocyclic cleavage of conformationally restricted pyranosides in the chair form was obtained by intra‐ and intermolecular Friedel–Crafts reactions, chloride addition, and reduction of the generated cation. On the other hand, pyranosides with the distorted conformation were never cleaved in an endocyclic manner.

  与其他吡喃糖苷相比，在存在路易斯酸的情况下，携带2，3-反式氨基甲酸酯和碳酸酯的吡喃糖苷很容易从β方向向α方向异构化。该反应是由吡喃糖苷的环内切割引起的。通过分子内和分子间Friedel-Crafts反应，添加氯化物和还原生成的阳离子，获得了椅型构象受限吡喃糖苷的环内裂解证据。另一方面，构象失真的吡喃糖苷从未以内环方式被裂解。