phenyl 4,6-di-O-benzyl-1-thio-β-D-glucopyranoside | 864966-92-7

• 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-1-thio-β-D-glucopyranoside
• 英文别名: (2S,3R,4R,5S,6R)-5-phenylmethoxy-6-(phenylmethoxymethyl)-2-phenylsulfanyloxane-3,4-diol
• CAS: 864966-92-7
• 化学式: C₂₆H₂₈O₅S
• 分子量: 452.571
• InChiKey: NSSPYKLQGZRHTI-SDVOOXDOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  32
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  93.4
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  phenyl 4,6-di-O-benzyl-1-thio-β-D-glucopyranoside 在 1-(苯基亚硫酰基)哌啶 、 三氟甲磺酸酐 、 三乙胺 、 2,4,6-三叔丁基嘧啶 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 2.5h， 生成 methyl 4-O-(4,6-di-O-benzyl-2,3-O-carbonyl-β-D-glucopyranosyl)-(1->4)-2,3-O-isopropylidene-α-L-rhamnopyranoside
  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
• 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 、 三氟乙酸 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 8.17h， 生成 phenyl 4,6-di-O-benzyl-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

• A 1,2-<i>trans</i> -Selective Glycosyl Donor Bearing Cyclic Protection at the C-2 and C-3 Hydroxy Groups
  作者：Nahoko Yagami、Hideki Tamai、Taro Udagawa、Akiharu Ueki、Miku Konishi、Akihiro Imamura、Hideharu Ishida、Makoto Kiso、Hiromune Ando

  DOI：10.1002/ejoc.201700671

  日期：2017.9.1

  A new 1,2-trans-selective glycosylation reaction is described. Glucosyl donors protected cyclically at the C-2 and C-3 hydroxy groups as six- (butane diacetal), seven- (tetraisopropyldisiloxanylidene), or eight- (2,3-o-xylylene) membered fused rings were synthesized in a straightforward manner. The glycosylation reactions of the glucosyl donors with various acceptors mainly generated β-glycosides under

  描述了一种新的 1,2-反式选择性糖基化反应。葡萄糖基供体在 C-2 和 C-3 羟基上被循环保护为六（丁烷二缩醛）、七（四异丙基二亚硅氧烷）或八（2,3-o-亚二甲苯基）元稠环，以直接方式合成. 在常规反应条件下，葡萄糖基供体与各种受体的糖基化反应主要生成β-糖苷。结果表明，从立体选择性和化学稳定性的角度来看，邻二甲苯基是合适的1,2-反式导向基团。通过核磁共振光谱和计算模拟对邻二甲苯保护的葡萄糖衍生物的氧代碳鎓离子进行了构象研究。结果表明氧碳鎓离子主要采用 4H3 构象，这是由于 C-2 和 C-3 处的刚性互稠环，而非环状保护的衍生物可能在构象之间波动。这些结果表明，C-2 处的伪赤道木氧基与传入的亲核试剂之间的相互作用阻碍了 1,2-顺式攻击。
• Stereoselective Synthesis of Diglycosyl Diacylglycerols with Glycosyl Donors Bearing a β-Stereodirecting 2,3-Naphthalenedimethyl Protecting Group
  作者：Nahoko Yagami、Amol M. Vibhute、Hide-Nori Tanaka、Naoko Komura、Akihiro Imamura、Hideharu Ishida、Hiromune Ando

  DOI：10.1021/acs.joc.0c02121

  日期：2020.12.18

  in the immune response systems. The chemical synthesis of DGDGs has been highly demanded, as it will allow the elucidation of their biological functions at the molecular level. In this study, we have developed a novel β-stereodirecting 2,3-naphthalenedimethyl (NapDM) protecting group that is orthogonal to protecting groups commonly used in oligosaccharide synthesis. The NapDM group can be easily cleaved

  二糖基二酰基甘油（DGDGs）是革兰氏阳性细菌质膜的主要成分，参与免疫应答系统。对DGDG的化学合成提出了很高的要求，因为它将允许在分子水平上阐明其生物学功能。在这项研究中，我们开发了一种新型的β-立体定向2,3-萘二甲基（NapDM）保护基，该保护基与寡糖合成中常用的保护基正交。在TFA介导的酸性条件下，NapDM基团很容易裂解。此外，我们通过利用NapDM基团合成DGDG证明了该保护基在无酰基保护基策略中的应用。
• Synthesis and Photochromic Properties of Azobenzene-Derived Glycomacrolactones
  作者：Chaoqi Lin、Stéphane Maisonneuve、Cyril Theulier、Juan Xie

  DOI：10.1002/ejoc.201801832

  日期：2019.2.28

  Photoswitchable and bistable glycomacrolactones: Azobenzene‐based glycomacrolactones have been synthesized from gluco and manno thioglycosides. These glycoazobenzenes display excellent photochromic properties and bistability. The E→Z photoisomerization induced a large change in the conformation and the chirality of the macrolactones. Both E‐ and Z‐glycomacrolactones show a (P) helical structure, as

  光开关和双稳态的糖基内酯：基于偶氮苯的糖基内酯是由葡萄糖和甘露糖基硫代糖苷合成的。这些糖基偶氮苯具有出色的光致变色性能和双稳性。该ê → ž光致异构引起的构象变化较大和大环内酯的手性。既ë -和Ž -glycomacrolactones示出了（P）螺旋结构，通过TD-DFT计算所建议的。
• 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.