methyl 2,3,4-tri-O-benzoyl-6-O-(2-deoxy-3,4,6-tri-O-acetyl-β-D-glucopyranosyl)-α-D-glucopyranoside | 627509-64-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,3,4-tri-O-benzoyl-6-O-(2-deoxy-3,4,6-tri-O-acetyl-β-D-glucopyranosyl)-α-D-glucopyranoside
• 英文别名: 2-deoxy-D-araHex3Ac4Ac6Ac(b1-6)[Bz(-2)][Bz(-3)][Bz(-4)]a-Glc1Me；[(2R,3R,4S,5R,6S)-4,5-dibenzoyloxy-2-[[(2R,4R,5S,6R)-4,5-diacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxymethyl]-6-methoxyoxan-3-yl] benzoate
• CAS: 627509-64-2
• 化学式: C₄₀H₄₂O₁₆
• 分子量: 778.764
• InChiKey: AEWGPJWZYDYAEQ-BDRIFYMWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  56
• 可旋转键数：
  20
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  195
• 氢给体数：
  0
• 氢受体数：
  16

反应信息

• 作为反应物：
  描述：

  methyl 2,3,4-tri-O-benzoyl-6-O-(2-deoxy-3,4,6-tri-O-acetyl-β-D-glucopyranosyl)-α-D-glucopyranoside 在 sodium methylate 作用下， 以 甲醇 为溶剂， 生成
  参考文献：
  名称：

  Glycosylation with 2′-thio-S-acetyl participation

  摘要：

  The reaction of 1,2,3,4,6-penta-O,S,O,O,O-acetyl-2-thio-beta-D-glucopyranose with glycosyl acceptors in the presence of trimethylsilyl triflate leads to the beta-disaccharides exclusively, owing to especially avid anchimeric assistance by the 2-thio-S-acetyl group. Optional reductive removal of -SAc with Ra-Ni gives the corresponding 2'-deoxy-beta-disaccharides. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2003.08.063
• 作为产物：
  描述：

  Acetic acid (2S,3R,4S,5R,6R)-2,5-diacetoxy-6-acetoxymethyl-3-trifluoromethanesulfonyloxy-tetrahydro-pyran-4-yl ester 在 三氟甲磺酸三甲基硅酯 、 镍 作用下， 以 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.5h， 生成 methyl 2,3,4-tri-O-benzoyl-6-O-(2-deoxy-3,4,6-tri-O-acetyl-β-D-glucopyranosyl)-α-D-glucopyranoside
  参考文献：
  名称：

  Glycosylation with 2′-thio-S-acetyl participation

  摘要：

  The reaction of 1,2,3,4,6-penta-O,S,O,O,O-acetyl-2-thio-beta-D-glucopyranose with glycosyl acceptors in the presence of trimethylsilyl triflate leads to the beta-disaccharides exclusively, owing to especially avid anchimeric assistance by the 2-thio-S-acetyl group. Optional reductive removal of -SAc with Ra-Ni gives the corresponding 2'-deoxy-beta-disaccharides. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2003.08.063

文献信息

• Characterization of the Isochromen-4-yl-gold(I) Intermediate in the Gold(I)-Catalyzed Glycosidation of Glycosyl ortho-Alkynylbenzoates and Enhancement of the Catalytic Efficiency Thereof
  作者：Yugen Zhu、Biao Yu

  DOI：10.1002/anie.201103409

  日期：2011.8.29

  Gold standard: The title gold complex (see scheme) was characterized unambiguously as an important intermediate in the title reaction. Protonolysis of this vinyl gold(I) complex was critical for regeneration of the active gold(I) species for the catalytic cycle, and use of a protic acid co‐catalyst significantly lowered the required catalyst loading to 0.5 mol %.

  金标准：标题金络合物（参见方案）被明确表征为标题反应中的重要中间体。该乙烯基金（I）配合物的质子分解对于活性金（I）物种在催化循环中的再生至关重要，并且使用质子酸助催化剂可将所需的催化剂负载量大大降低至0.5 mol％。
• Direct and Stereoselective Synthesis of α-Linked 2-Deoxyglycosides
  作者：Jin Park、Thomas J. Boltje、Geert-Jan Boons

  DOI：10.1021/ol801833n

  日期：2008.10.2

  alpha-Linked 2-deoxyglycosides were conveniently obtained by employing a glycosyl donor having a participating ( S)-(phenylthiomethyl)benzyl moiety at C-6, whereas 2,6-dideoxy-alpha-glycosides could be prepared by BF 3.Et 2O-promoted activation of allyl glycosyl donors.

  α-连接的 2-脱氧糖苷可以通过使用在 C-6 处具有参与 (S)-(苯硫基甲基) 苄基部分的糖基供体方便地获得，而 2,6-双脱氧-α-糖苷可以通过 BF 3.Et 2O 制备- 促进烯丙基糖基供体的活化。
• GeCl₂·Dioxane–AgBF₄ Catalyzed Activation of Glycosyl Fluorides for Glycosylation
  作者：Qiuyu Zhu、Yu Tang、Biao Yu

  DOI：10.1021/acs.orglett.2c01146

  日期：2022.5.27

  catalytic glycosyl fluoride activation system using the GeCl2·dioxane–AgBF4 combination was developed, which involves a reversible activation of the anomeric C–F bond by a [Ge(II)–Cl]+ cation and a reversible chloride ion transfer between Ge(II) and glycosyl cations. This catalytic glycosylation system is easy to operate, proceeds at room temperature, and offers a broad scope of substrates.

  开发了一种使用 GeCl 2 ·二恶烷-AgBF 4组合的催化糖基氟化物活化系统，该系统涉及通过 [Ge(II)-Cl] +阳离子对异头 C-F 键的可逆活化和在它们之间的可逆氯离子转移。 Ge(II) 和糖基阳离子。这种催化糖基化系统易于操作，在室温下进行，并提供广泛的底物。
• Gold-Catalyzed Synthesis of 2-Deoxy Glycosides Using <i>S</i>-But-3-ynyl Thioglycoside Donors
  作者：Surya Adhikari、Kedar N. Baryal、Danyang Zhu、Xiaohua Li、Jianglong Zhu

  DOI：10.1021/cs300670k

  日期：2013.1.4

  A mild and atom-economic gold(I)-catalyzed glycosylation for stereoselective synthesis of 2-deoxy alpha-glycosides using bench-stable 2-deoxy S-But-3-ynyl thioglycoside donors has been described. Under optimal conditions, 2-deoxy and 2,6-dideoxy thioglycoside donors were able to react with a variety of primary, secondary, and tertiary alcohol acceptors to afford alpha-selective glycosides in good to excellent yields.
• A One-Pot Method for Removal of Thioacetyl Group via Desulfurization under Ultraviolet Light To Synthesize Deoxyglycosides
  作者：Jian-Tao Ge、Lang Zhou、Tao Luo、Jian Lv、Hai Dong

  DOI：10.1021/acs.orglett.9b02033

  日期：2019.8.2

  We herein developed an efficient method for removing thioacetyl to synthesize acylated deoxy glycosides in a one-pot reaction, where the thioacetyl was selectively deacetylated by hydrazine hydrate in DMF within 2-5 min at room temperature, followed by desulfurization under UV light for 1-2 h in the presence of TCEP center dot HCl. The method was then used to synthesize 2-deoxy glycosides with absolute alpha/beta-configuration via stereoselective control of C-2 thioacetate in glycosylation.