methyl 4-O-acetyl-6-O-tert-butyldiphenylsilyl-α-D-glucopyranoside | 130359-43-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 4-O-acetyl-6-O-tert-butyldiphenylsilyl-α-D-glucopyranoside
• 英文别名: [(2R,3S,4R,5R,6S)-2-[[tert-butyl(diphenyl)silyl]oxymethyl]-4,5-dihydroxy-6-methoxyoxan-3-yl] acetate
• CAS: 130359-43-2
• 化学式: C₂₅H₃₄O₇Si
• 分子量: 474.626
• InChiKey: JPQXGLOUSLOJKV-RMRNXIRCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.59
• 重原子数：
  33.0
• 可旋转键数：
  7.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  94.45
• 氢给体数：
  2.0
• 氢受体数：
  7.0

反应信息

• 作为产物：
  描述：

  alpha-甲基葡萄糖甙 在 咪唑 、 4-二甲氨基吡啶 、 potassium carbonate 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 17.0h， 生成 methyl 4-O-acetyl-6-O-tert-butyldiphenylsilyl-α-D-glucopyranoside
  参考文献：
  名称：

  Directing-protecting groups for carbohydrates. Design, conformational study, synthesis and application to regioselective functionalization

  摘要：

  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.

  DOI：

  10.1016/j.tet.2005.04.060

文献信息

• Novel methods for the preparation of partially acetylated carbohydrates
  作者：Stephen Hanessian、Masahiro Kagotani

  DOI：10.1016/0008-6215(90)84071-2

  日期：1990.7

  Abstract The selective acetylation of methyl a - d -hexopyranosides in the presence of zinc chloride shows unusual reactivity patterns compared to control experiments. Hydroperoxide ion is a mild and selective deacetylation reagent which does not attack primary acetates.

  摘要在氯化锌存在下，甲基α-d-己吡喃糖苷的选择性乙酰化与对照实验相比，显示出不同寻常的反应模式。氢过氧化物离子是一种温和的，选择性的脱乙酰基试剂，不会侵蚀初级乙酸盐。
• HANESSIAN, STEPHEN;KAGOTANI, MASAHIRO, CARBOHYDR. RES., 202,(1990) C. 67-79
  作者：HANESSIAN, STEPHEN、KAGOTANI, MASAHIRO

  DOI：——

  日期：——