Acetic acid (2R,3S,4R,5R,6S)-4,5-dihydroxy-6-methoxy-2-trityloxymethyl-tetrahydro-pyran-3-yl ester | 53716-96-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: Acetic acid (2R,3S,4R,5R,6S)-4,5-dihydroxy-6-methoxy-2-trityloxymethyl-tetrahydro-pyran-3-yl ester
• 英文别名: [(2R,3S,4R,5R,6S)-4,5-dihydroxy-6-methoxy-2-(trityloxymethyl)oxan-3-yl] acetate
• CAS: 53716-96-4
• 化学式: C₂₈H₃₀O₇
• 分子量: 478.542
• InChiKey: QFWOXEXVKRKVPU-ACFIUOAZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  35
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  94.4
• 氢给体数：
  2
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  Acetic acid (2R,3S,4R,5R,6S)-4,5-dihydroxy-6-methoxy-2-trityloxymethyl-tetrahydro-pyran-3-yl ester 在 copper(II) sulfate 作用下， 以 苯 为溶剂， 反应 5.0h， 以98%的产率得到methyl 4-O-acetyl-α-D-glucopyranoside
  参考文献：
  名称：

  A simple method for detritylation of carbohydrate derivatives

  摘要：

  DOI：

  10.1016/s0008-6215(00)84678-9
• 作为产物：
  描述：

  乙酸酐 、 甲基-6-O-三苯基甲基-alpha-D-吡喃葡萄糖苷 在 C₂₇H₃₉N₇ 作用下， 以 氯仿 为溶剂， 以62 %的产率得到methyl 3-O-acetyl-6-O-trityl-α-D-glucopyranoside
  参考文献：
  名称：

  三价二烷基氨基吡啶催化部分保护的吡喃苷的位点选择性单-O-酰化

  摘要：

  这项工作证明了三价三-(3- N-甲基-N-吡啶基丙基)胺( 1 )催化吡喃糖苷的位点选择性单-O-酰化。在催化剂1的介导下，使用不同的酸酐对单糖进行酰化，负载量为 1.5 mol%；评估了位点选择性的程度和单-O-酰化产物的产率。反应进行 2 至 10 小时，具体取决于酸酐的性质，其中体积较大的新戊酸酐需要较长的酰化时间。吡喃糖苷保持为二醇和三醇，并且从一组实验中观察到酰化的位点选择性遵循羟基官能团的内在反应性和立体化学。与一价N , N-二甲氨基吡啶 (DMAP) 催化剂相比，三价催化剂1在所研究的吡喃糖苷中以优异的位点选择性介导单-O-酰化产物形成的反应。这项研究说明了催化部分的多价性的好处。

  DOI：

  10.1039/d4ob00599f

文献信息

• Modulation of the relative reactivities of carbohydrate secondary hydroxyl groups. Modification of the hydrogen bond network
  作者：Nicolas Moitessier、Yves Chapleur

  DOI：10.1016/s0040-4039(03)00141-2

  日期：2003.2

  An approach towards the control of the relative regioselectivity of the secondary hydroxyl groups is presented. Original protecting groups, which are capable of specific intramolecular hydrogen bonds and are likely to modulate the partial charges of the oxygen atoms, have been developed. Qualitative NMR experiments confirmed the existence of the expected hydrogen bonds and shed light on the perturbation of the cooperative intramolecular hydrogen bond network. Further reactivity studies are presented and confirm the potential of protecting group-mediated regioselective functionalization of carbohydrates. (C) 2003 Elsevier Science Ltd. All rights reserved.
• Directing-protecting groups for carbohydrates. Design, conformational study, synthesis and application to regioselective functionalization
  作者：Nicolas Moitessier、Pablo Englebienne、Yves Chapleur

  DOI：10.1016/j.tet.2005.04.060

  日期：2005.7

  A novel concept of regioselective transformation of secondary hydroxyl groups in carbohydrates is presented. First, the relative reactivity of the free hydroxyl groups of onoprotected D-glucose derivatives was assessed using acetylation as a model reaction. As a result, acylation of these polyols gave it mixture of monosubstituted products in which the 3-O functionalized derivatives predominated. Novel hydrogen bond acceptor protecting groups were next designed to modulate the 4-OH and 3-OH reactivity in the hope to mediate higher regioselective transformations. A molecular modeling study later validated by spectroscopic analysis predicted additional intramolecular hydrogen bonds between the hydroxyl groups and pyridyl-containing protecting groups. Taking advantage of this induced hydrogen bond network. we achieved regioselective acetylation of the hydroxyl group at position 3 without protecting any secondary hydroxyl groups of the carbohydrate moiety. This designed protecting/directing group increased the nucleophilicity and the steric hindrance of position 3. As a result, optimization of the reaction conditions enabled the monoacetylation (not affected by steric hindrance) of 6-O-protected,glucopyranosides at position 3 and selective silylation (affected by steric hindrance) of position 2 in high isolated yields and regioselectivities. This result certainly opens doors to the regioselective open glycosylation of carbohydrates. (c) 2005 Elsevier Ltd. All rights reserved.