methyl 6-O-acetyl-α-D-glucopyranoside | 4201-66-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 6-O-acetyl-α-D-glucopyranoside
• 英文别名: [(2R,3S,4S,5R,6S)-3,4,5-trihydroxy-6-methoxyoxan-2-yl]methyl acetate
• CAS: 4201-66-5
• 化学式: C₉H₁₆O₇
• 分子量: 236.222
• InChiKey: PBSHTCWJMNLCFN-ZEBDFXRSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -2
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  105
• 氢给体数：
  3
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl 6-O-acetyl-α-D-glucopyranoside 、 乙酸酐 在 4-二甲氨基吡啶 、 potassium carbonate 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 生成 2,6-di-O-Ac-α-D-Glc 、 2,2-dichloro-4,4,6,6-tetramethyl-1,3,5,2,4,6-trioxatrisilinane 、 methyl 3,6-di-O-acetyl-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
• 作为产物：
  描述：

  2,3,4,6-四-o-乙酰基-alpha-d-吡喃葡萄糖苷甲酯 生成 methyl 6-O-acetyl-α-D-glucopyranoside
  参考文献：
  名称：

  HERZIG, JACOB;NUDELMAN, ABRAHAM;GOTTLIEB, HUGO E., CARBOHYDR. RES., 177,(1988) 21-28

  摘要：

  DOI：

文献信息

• Regioselective acetylation of carbohydrates and diols catalyzed by tetramethyl-ammonium hydroxide in water
  作者：Yuchao Lu、Peng Wei、Yuxin Pei、Hengfu Xu、Xiaoting Xin、Zhichao Pei

  DOI：10.1039/c4gc00770k

  日期：——

  A novel method for an efficient regioselective acetylation of carbohydrates and diols in aqueous solution is described. Treatment of substrates with 1-acetylimidazole, and tetramethyl-ammonium hydroxide (TMAH) in water under mild conditions gave highly regioselective acetylation for primary hydroxyl groups. This discovery provides an eco-friendly way for selective acetylation of non-protected glycosides

  描述了一种用于在水溶液中有效地对碳水化合物和二醇进行区域选择性乙酰化的新方法。在温和的条件下，在水中用1-乙酰基咪唑和氢氧化四甲基铵（TMAH）处理底物，可得到伯羟基的高度区域选择性乙酰化。该发现为水中非保护的糖苷和二醇的选择性乙酰化提供了一种环保的方法，避免了使用有毒有机溶剂和避免对仲羟基进行预保护的必要性。
• Carbohydrate esterases of family 2 are 6-<i>O</i>-deacetylases
  作者：Evangelos Topakas、Sarantos Kyriakopoulos、Peter Biely、Ján Hirsch、Christina Vafiadi、Paul Christakopoulos

  DOI：10.1016/j.febslet.2009.11.095

  日期：2010.2.5

  regioselectivity is different from that of typical acetylxylan esterases (AcXEs). In aqueous medium saturated with vinyl acetate, the CE‐2 enzymes catalyzed transacetylation to the same position, i.e., to the primary hydroxyl group of mono‐ and disaccharides. Xylose and xylooligosaccharides did not serve as acetyl group acceptors, therefore the CE‐2 enzymes appear to be 6‐O‐deacetylases.

  测试了来自腐生细菌 Cellvibrio japonicus 和热纤梭菌（碳水化合物酯酶 (CE) 家族 2 的成员）的三种乙酰酯酶 (AcE) 对一系列模型底物的活性，包括部分乙酰化的葡萄糖苷、甘露糖苷和吡喃木糖苷。所有三种酶都表现出对己醛糖 6 位脱乙酰化的强烈偏好。这种区域选择性不同于典型的乙酰木聚糖酯酶 (AcXE)。在醋酸乙烯饱和的水性介质中，CE-2 酶催化乙酰基转移到相同的位置，即到单糖和二糖的伯羟基。木糖和低聚木糖不作为乙酰基受体，因此 CE-2 酶似乎是 6-O-脱乙酰酶。
• Methanolysis of acetylated sugars and glycosides in the presence of tin oxides and alkoxides
  作者：Jacob Herzig、Abraham Nudelman、Hugo E. Gottlieb

  DOI：10.1016/0008-6215(88)85038-9

  日期：1988.6

  Abstract A simple, regioselective O -deacetylation procedure is described which involves ⩽0.5 equiv. of Bu 3 SnOMe or Bu 2 SnO in methanol. Anomeric acetates are considerably more reactive than primary and secondary acetates, thereby enabling selective removal, to give ∼70% of products with HO-1 unsubstituted. Prolonged reaction resulted in complete deacetylation. Secondary acetates were removed faster

  摘要描述了一种简单的区域选择性O-脱乙酰化方法，涉及involves0.5当量。甲醇中的Bu 3 SnOMe或Bu 2 SnO的混合物。端粒的乙酸盐比起伯乙酸盐和仲乙酸盐具有更高的反应活性，因此能够选择性地除去，从而得到约70％的HO-1未取代的产物。长时间的反应导致完全脱乙酰。仲乙酸盐的去除速度比伯乙酸盐更快，并且反应的总速率受OAc OH⪢OMe顺序的异头取代基影响很大。在反应条件下没有酰基迁移发生。
• A novel enzymatic method for the synthesis of methyl 6-O-acetyl-α-d-glucopyranoside using a fermented solid containing lipases produced by Burkholderia contaminans LTEB11
  作者：Maribel Cordero Villalobos、Alan Guilherme Gonçalves、Miguel Daniel Noseda、David Alexander Mitchell、Nadia Krieger

  DOI：10.1016/j.procbio.2018.07.023

  日期：2018.10

  Enzymatic methods are promising since they can give high selectivity in a single step. We developed a new method for acetylation of methyl-α- d -glucopyranoside with vinyl acetate, the reaction being catalyzed by a fermented solid containing lipases from Burkholderia contaminans LTEB11. The main product of the synthesis, methyl 6-O-acetyl-α- d -glucopyranoside (6-OAc-α-MetGlc), was identified by NMR and quantified

  摘要 碳水化合物区域选择性修饰的化学方法需要几个步骤，包括添加和去除保护基团。酶促方法很有前景，因为它们可以在一个步骤中提供高选择性。我们开发了一种用乙酸乙烯酯乙酰化甲基-α-d-吡喃葡萄糖苷的新方法，该反应由含有来自污染伯克霍尔德菌 LTEB11 的脂肪酶的发酵固体催化。合成的主要产物甲基 6-O-乙酰基-α-d-吡喃葡萄糖苷 (6-OAc-α-MetGlc) 通过 NMR 进行鉴定并通过 HPLC 进行定量。在不同溶剂系统中以实验室规模 (4 mL) 评估甲基-α-d-吡喃葡萄糖苷向 6-OAc-α-MetGlc 的转化。转化率随着溶剂疏水性的增加而增加，转化率最高，72 h 达到 65%，在无溶剂体系中获得。该系统放大到 1 L 反应介质。在 72 小时内获得了 76% 的转化率，计算出的 6-OAc-α-MetGlc 产量为 1.05 g (4.43 mmol)。这是迄今为止文献中报道的由酶催化产生的最大量的
• Regioselective Deacetylation of Fully Acetylated Mono- and Di-Saccharides With Hydrazine Hydrate
  作者：R Khan、PA Konowicz、L Gardossi、M Matulova、S Degennaro

  DOI：10.1071/ch9960293

  日期：——

  Selective deacetylation reactions of the peracetylated reducing disaccharides (1), (5), (9), (15), β-D- glucopyranose (17) and 2-acetamido-2-deoxy-β-D-glucopyranose (19), with 1.2 equiv. Of hydrazine hydrate in acetonitrile, gave predominantly the corresponding heptaacetates (2), (6), (10), (16), the tetraacetate (18) and the triacetate (20), with the free hydroxy group at C1. Reaction of (1) with 1.2 equiv. of hydrazine hydrate in N,N- dimethylformamide also afforded the heptaacetate (2), but in lower yield. When reactions of (1), (5) and (9) were performed with 2.5 equiv. of hydrazine hydrate, deacetylation also occurred at other positions to afford the corresponding hexaacetates (3), (7), (11) and (12), with hydroxy groups at C 1,2 or C 1,3, and the pentaacetates (4), (8) and (13), with hydroxy groups at C 1,2,3. Maltose octaacetate (9), in addition, yielded the tetraacetate (14) in which the free hydroxy groups were located at C1,2,2',3. Compound (15) on treatment with 2.5 equiv. of hydrazine hydrate afforded an intractable mixture. The reaction of methyl 2,3,4,6-tetra-O-acetyl-α-D-glucopyranoside (21) with 2.5 equiv. of hydrazine hydrate gave the 3,4,6-triacetate (22), a mixture of the 2,6- and the 3,6-diacetates (23) and (24), respectively, the 4,6-diacetate (25), and the 6-acetate (26).

  过乙酰化还原二糖 (1)、(5)、(9)、(15)、β-D-吡喃葡萄糖 (17) 和 2-乙酰氨基-2-脱氧-β-D-吡喃葡萄糖 (19) 与 1.2 等当量的肼水合物在乙腈中进行选择性脱乙酰化反应，主要得到相应的七乙酸酯 (2)、(6)、(10)、(16)、四乙酸酯 (18)乙腈中的水合肼反应，主要得到相应的七乙酸酯（2）、（6）、（10）、（16）、 四乙酸酯（18）和三乙酸酯（20），其游离羟基位于 C1。将(1)与 1.2 等量的水合肼在 N,N-二甲基甲酰胺中反应，也能得到庚乙酸酯(2)，但产量较低。当用 2.5 等量的水合肼对(1)、(5)和(9)进行反应时，在其他位置也会发生脱乙酰化反应，从而得到相应的六乙酸酯(3)、(7)、(11)和(12)（羟基位于 C 1,2 或 C 1,3）以及五乙酸酯(4)、(8)和(13)（羟基位于 C 1,2,3）。此外，麦芽糖八乙酸酯（9）可生成四乙酸酯（14），其中的游离羟基位于 C1,2,2',3。化合物 (15) 在与 2.5 等量的水合肼处理后，生成了一种难溶于水的混合物。2,3,4,6-O-四乙酰基-α-D-吡喃葡萄糖苷甲酯 (21) 与 2.5 等量的水合肼反应，得到 3,4,6-三乙酸酯 (22)、分别为 2,6- 和 3,6- 二乙酸酯 (23) 和 (24) 的混合物、4,6-二乙酸酯 (25) 和 6- 乙酸酯 (26)。