o-cresyl 2-deoxy-3,4,6-tri-O-benzyl-β-D-gluco-pyranoside | 136174-88-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: o-cresyl 2-deoxy-3,4,6-tri-O-benzyl-β-D-gluco-pyranoside
• 英文别名: o-cresyl 3,4,6-tri-O-benzyl-2-deoxy-β-D-glucopyranoside；(2R,3S,4R,6S)-6-(2-methylphenoxy)-3,4-bis(phenylmethoxy)-2-(phenylmethoxymethyl)oxane
• CAS: 136174-88-4
• 化学式: C₃₄H₃₆O₅
• 分子量: 524.657
• InChiKey: FJDNXDBWGHKAFE-PZMYXVABSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.6
• 重原子数：
  39
• 可旋转键数：
  12
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  46.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  3,4,6-三-氧-苄基-2-脱氧-D-吡喃葡萄糖 在 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 、 二乙二醇二甲醚 为溶剂， 反应 19.5h， 生成 o-cresyl 2-deoxy-3,4,6-tri-O-benzyl-β-D-gluco-pyranoside
  参考文献：
  名称：

  2-脱氧糖与试剂的β-特异性脱水糖基化反应

  摘要：

  N-磺酰基咪唑可能通过将它们原位转化为糖基磺酸盐而活化2-脱氧糖半缩醛以进行糖基化。通过使磺酸盐的离去基团能力与供体的反应性匹配，可以获得β特异性糖基化反应。该反应证明了原理，即通过选择可以调节活性中间体反应性的启动子，可以将糖基化反应完全置于试剂的控制之下。

  DOI：

  10.1021/ol4018547

文献信息

• Reagent-Controlled Stereoselective Glycosylation
  申请人：Trustees of Tufts College

  公开号：US20150038689A1

  公开（公告）日：2015-02-05

  Provided are methods for the efficient stereoselective formation of glycosidic bonds, without recourse to prosthetic or directing groups.

  提供了一种高效立体选择性形成糖苷键的方法，无需使用假体或定向基团。
• Studies on the Synthesis of Aureolic Acid Antibiotics: Highly Stereoselective Synthesis of Aryl 2-Deoxy-.beta.-glycosides via the Mitsunobu Reaction and Synthesis of the Olivomycin A-B Disaccharide
  作者：William R. Roush、Xiao-Fa Lin

  DOI：10.1021/ja00113a013

  日期：1995.3

  The Mitsunobu reaction of phenols and 1,2-cis-2-thiophenyl-alpha-D-glycopyranoses or 1,2-cis-2-selenophenyl-alpha-D-glycopyranoses is a very effective method for the highly stereoselective synthesis of aryl 2-deoxy-beta-D-glycosides. The equatorial 2-thiophenyl or 2-selenophenyl- substituents are easily removed by Bu(3)SnH reduction following the glycosidation reaction to provide the aryl 2-deoxy-beta-D-glycosides in good to excellent yield. The aryl beta-D-glycosides are obtained with 6.5:1 selectivity in the least selective case(Table 1) and up to >20:1 selectivity in others. The reaction appears to be S-N(2)-like in character (see 30), in that the beta:alpha reaction stereoselectivity correlates well with the alpha:beta anomeric composition of the pyranose starting material. The equatorial 2-thiophenyl or 2-selenophenyl substituents play an important role by increasing the alpha:beta anomer ratio of the pyranose starting materials. The reactions do not appear to proceed by way of free oxonium ions such as 17, since several reactions in which 17 was deliberately generated (e.g., TMS-OTf promoted reactions of glycosyl acetate 14, BF3 . Et(2)O catalyzed reactions of imidate 15) gave at best 1:1 mixtures of alpha- and beta-glycosides, and in several cases gave alpha-glycosides with >10:1 selectivity. These data also rule out the involvement of episulfonium ion 18 as a kinetically significant intermediate in reactions that proceed by way of oxonium ion 17. A short and highly effective synthesis of reducing disaccharide 53 from D-fucal was developed. This functionalized disaccharide readily undergoes Mitsunobu glycosidation with 2-naphthol, providing the model naphthyl A-B disaccharide 5 with 11:1 beta,alpha:alpha,alpha selectivity. Finally, olivin precursor 63 has also been glycosylated with 53, providing the advanced synthetic intermediate 6 with excellent diastereoselectivity.
• A highly stereoselective synthesis of aryl 2-deoxy-.beta.-glycosides via the Mitsunobu reaction
  作者：William R. Roush、Xiao Fa Lin

  DOI：10.1021/jo00020a003

  日期：1991.9

  A highly stereoselective (6.5- > 20:1) synthesis of aryl 2-deoxy-beta-D-glycosides is described. This method involves the Mitsunobu coupling of phenols and 2-alpha-(thiophenyl)- or 2-alpha-(selenophenyl)-alpha-D-pyranoses 3-6, 18, and 19 followed by Bu3SnH reduction of the PhS- and PhSe-groups.
• Reagent Controlled β-Specific Dehydrative Glycosylation Reactions with 2-Deoxy-Sugars
  作者：John Paul Issa、Dina Lloyd、Emily Steliotes、Clay S. Bennett

  DOI：10.1021/ol4018547

  日期：2013.8.16

  2-deoxy-sugar hemiacetals for glycosylation presumably by converting them into glycosyl sulfonates in situ. By matching the leaving group ability of the sulfonate with the reactivity of the donor, it is possible to obtain β-specific glycosylation reactions. The reaction serves as proof of the principle that, by choosing promoters that can modulate the reactivity of active intermediates, it is possible to place

  N-磺酰基咪唑可能通过将它们原位转化为糖基磺酸盐而活化2-脱氧糖半缩醛以进行糖基化。通过使磺酸盐的离去基团能力与供体的反应性匹配，可以获得β特异性糖基化反应。该反应证明了原理，即通过选择可以调节活性中间体反应性的启动子，可以将糖基化反应完全置于试剂的控制之下。