methyl α-D-galacto-hexodialdo-1,5-pyranoside | 35094-55-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl α-D-galacto-hexodialdo-1,5-pyranoside
• 英文别名: Methyl-α-D-galacto-hexodialdopyranosid；Methyl-α-D-galacto-hexodialdo-1,5-pyranosid；(2S,3R,4S,5R,6S)-3,4,5-trihydroxy-6-methoxyoxane-2-carbaldehyde
• CAS: 35094-55-4
• 化学式: C₇H₁₂O₆
• 分子量: 192.169
• InChiKey: HQELTDCENJWLGH-PZRMXXKTSA-N

物化性质

• 沸点：
  377.2±42.0 °C(Predicted)
• 密度：
  1.46±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -1.9
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  96.2
• 氢给体数：
  3
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl α-D-galacto-hexodialdo-1,5-pyranoside 在 硼氘化钠 作用下， 以91 mg的产率得到C₇H₁₃⁽²⁾HO₆
  参考文献：
  名称：

  Oxidation of Polysaccharides by Galactose Oxidase

  摘要：

  Galactose oxidase was used as a catalyst to oxidize selectively the C-6 hydroxyls of terminal galactose to carbonyl groups. The polysaccharides studied included spruce galactoglucomannan, guar galactomannan, larch arabinogalactan, corn fiber arabinoxylan, and tamarind seed xyloglucan, with terminal galactose contents varying from 6% to 40%. A multienzyme system was used, with catalase and horseradish peroxidase to enhance the action of galactose oxidase. An analysis technique was developed for the quantification of the reactive aldehydes with GC-MS, utilizing NaBD4 reduction and acidic methanolysis. The best oxidation degrees of terminal galactosyls were obtained with xyloglucan (85% of galactose) and spruce galactoglucomannan (65% of galactose). The highest oxidation degree based on total carbohydrates was achieved with guar gum (28%), which had the highest galactose content. The oxidation resulted in changes in the physicochemical properties of the polysaccharide solutions, and the changes observed varied between the polysaccharides. The clearest change was in tamarind xyloglucan, which formed a gel after the oxidation. After the oxidation, larger particles were present in the solution of spruce galactoglucomannan, but changes in its rheological properties were not observed.

  DOI：

  10.1021/jf902930t
• 作为产物：
  描述：

  Α-D-乳酸吡喃糖苷甲酯 在 galactose oxidase M₁ 、 copper(II) sulfate 、 catalase 作用下， 生成 methyl α-D-galacto-hexodialdo-1,5-pyranoside
  参考文献：
  名称：

  半乳糖氧化酶的电化学活化：机理研究和合成应用

  摘要：

  半乳糖氧化酶 (GOase) 是一种铜自由基氧化酶，可催化伯醇有氧氧化为醛，并已在大规模制药过程中用于此目的。为了保持其催化活性并确保高底物转化率，GOase 需要通过 1e 连续（重新）激活-将不断形成的非循环物种（GOase semi）氧化为催化活性状态（GOase ox）。在这项工作中，我们报告了一种 GOase 的电化学活化方法，该方法在 GOase 催化的氧化反应中取代了以前使用的昂贵的辣根过氧化物酶激活剂。一、GOase牛的形成通过 GOase semi 的非酶促氧化生成专门设计的变体通过紫外-可见光谱研究。其次，使用循环伏安法研究了介体对 GOase 的电化学氧化。测定了不同 pH 值下 GOase 和各种介体之间的电子转移速率，显示出对介体的氧化还原电位和 pH 值的依赖性。这一观察结果表明，在 pH 7-9 时，介质对 GOase 的氧化可能是在厌氧条件下通过协调的质子耦合电子转移

  DOI：

  10.1021/acscatal.1c01037

文献信息

• Metal-mediated allylation of enzymatically oxidized methyl α-d-galactopyranoside
  作者：Ann-Sofie Leppänen、Outi Niittymäki、Kirsti Parikka、Maija Tenkanen、Patrik Eklund、Rainer Sjöholm、Stefan Willför

  DOI：10.1016/j.carres.2010.09.026

  日期：2010.12

  The C-6 unit of methyl alpha-D-galactopyranoside was selectively modified by combining enzymatic oxidation with an indium-mediated allylation reaction. The Barbier-Grignard type reaction, where a carbonyl group reacts with an allyl halide, proceeds in aqueous solution, even with water as the only solvent; thus carbohydrates can be modified without the need for drying or protection-deprotection steps

  甲基α-D-吡喃半乳糖苷的C-6单元是通过将酶促氧化与铟介导的烯丙基化反应相结合而选择性修饰的。Barbier-Grignard型反应（羰基与烯丙基卤反应）在水溶液中进行，即使只有水作为唯一溶剂也是如此。因此，无需干燥或保护-脱保护步骤即可对碳水化合物进行改性。在与烯丙基溴和肉桂酰氯的反应中，以＞ 90％的高产率产生相应的烯丙基醇。分离出主要产物，并通过GC-MS和NMR光谱进行表征。
• Cyclometallated Gold(III) Complexes as Effective Catalysts for Synthesis of Propargylic Amines, Chiral Allenes and Isoxazoles
  作者：Karen Ka-Yan Kung、Vanessa Kar-Yan Lo、Hok-Ming Ko、Gai-Li Li、Pui-Ying Chan、King-Chi Leung、Zhongyuan Zhou、Ming-Zhong Wang、Chi-Ming Che、Man-Kin Wong

  DOI：10.1002/adsc.201300005

  日期：2013.7.8

  were achieved in chiral allene synthesis. Chiral allene racemization could be minimized by using 1f as catalyst. The PEG‐linked catalyst 1m is the most catalytically active towards synthesis of propargylic amines, in which case a product turnover of 900 was achieved. Moreover, 1m could be repeatedly used for 12 reaction cycles, leading to an overall turnover number of 872.

  合成了一系列环金属化的金（III）配合物[Au（）Cl 2 ] 1a – 1（H =芳基吡啶）和PEG连接的配合物1m。配合物1a – m可有效催化炔丙基胺，手性烯丙基和异恶唑的合成。六元环环金属化金（III）配合物1f – l比五元环环金属化金（III）配合物1a – e具有更高的催化活性。可以通过使用手性醛和/或胺底物来调节炔丙基胺的非对映选择性。优异的对映选择性（90–98％ee）是在手性丙二烯合成中获得的。通过使用1f作为催化剂，手性烯丙基外消旋化作用可以减至最小。PEG连接的催化剂1m对炔丙基胺的合成具有最强的催化活性，在这种情况下，产品周转量达到900。此外，1m可重复使用12个反应周期，因此总周转数为872。
• Mono-N-glycosidation ofβ-Cyclodextrin− Synthesis of 6-(β-Cyclodextrinylamino)-6-deoxy-D-galactosides and ofN-(6-Deoxy-β-cyclodextrinyl)galacto-azepane
  作者：Véronique Bonnet、Raphaël Duval、Vinh Tran、Claude Rabiller

  DOI：10.1002/ejoc.200300449

  日期：2003.12

  reductive amination in the presence of NaBH3CN in DMSO. When methyl α-D- and p-nitrophenyl α- and β-D-galacto-hexodialdo-1,5-pyranosides (1, 2 and 3, respectively) were used as substrates, 6-(β-cyclodextrinylamino)-6-deoxy-D-galactopyranosides were obtained in 25−50% yields. The same was true in the cases of 6II-oxolactose 4 and of 6II-oxomelibiose 5, for which the anomeric carbon was shown to be unreactive

  通过半乳糖氧化酶介导的氧化反应生成 6-氧代半乳糖和 6-氧代半乳糖苷的简单途径允许在 DMSO 中存在 NaBH3CN 的情况下通过还原胺化使 6-氨基-6-脱氧-β-环糊精 N-糖苷化。当甲基 α-D- 和对硝基苯基 α- 和 β-D-galacto-hexodialdo-1,5-pyranosides（分别为 1、2 和 3）用作底物时，6-(β-环糊精氨基)-6-脱氧-D-吡喃半乳糖苷的产率为 25-50%。在 6II-氧代乳糖 4 和 6II-氧代糖二糖 5 的情况下也是如此，对于它们，异头碳在与 DMSO 的络合中表现出无反应性。该反应也成功地应用于含有氧化聚半乳甘露聚糖 6 的水中。半乳糖-己二醛-1,5-吡喃糖 7 的行为不同，因为进一步的分子内环化和还原以良好的产率产生 N-（6-脱氧-β-环糊精基）-半乳糖-氮杂环庚烷。分子模型也被用来解释这个反应的过程。计算表明7的中
• Electrochemical Activation of Galactose Oxidase: Mechanistic Studies and Synthetic Applications
  作者：Shaoguang Zhang、Serge Ruccolo、Anna Fryszkowska、Artis Klapars、Nicholas Marshall、Neil A. Strotman

  DOI：10.1021/acscatal.1c01037

  日期：2021.6.18

  The enzyme galactose oxidase (GOase) is a copper radical oxidase that catalyzes the aerobic oxidation of primary alcohols to the aldehydes and has been utilized to that end in large-scale pharmaceutical processes. To maintain its catalytic activity and ensure high substrate conversion, GOase needs to be continuously (re)activated by 1e– oxidation of the constantly formed out-of-cycle species (GOasesemi)

  半乳糖氧化酶 (GOase) 是一种铜自由基氧化酶，可催化伯醇有氧氧化为醛，并已在大规模制药过程中用于此目的。为了保持其催化活性并确保高底物转化率，GOase 需要通过 1e 连续（重新）激活-将不断形成的非循环物种（GOase semi）氧化为催化活性状态（GOase ox）。在这项工作中，我们报告了一种 GOase 的电化学活化方法，该方法在 GOase 催化的氧化反应中取代了以前使用的昂贵的辣根过氧化物酶激活剂。一、GOase牛的形成通过 GOase semi 的非酶促氧化生成专门设计的变体通过紫外-可见光谱研究。其次，使用循环伏安法研究了介体对 GOase 的电化学氧化。测定了不同 pH 值下 GOase 和各种介体之间的电子转移速率，显示出对介体的氧化还原电位和 pH 值的依赖性。这一观察结果表明，在 pH 7-9 时，介质对 GOase 的氧化可能是在厌氧条件下通过协调的质子耦合电子转移
• Oxidation of Polysaccharides by Galactose Oxidase
  作者：Kirsti Parikka、Ann-Sofie Leppänen、Leena Pitkänen、Markku Reunanen、Stefan Willför、Maija Tenkanen

  DOI：10.1021/jf902930t

  日期：2010.1.13

  Galactose oxidase was used as a catalyst to oxidize selectively the C-6 hydroxyls of terminal galactose to carbonyl groups. The polysaccharides studied included spruce galactoglucomannan, guar galactomannan, larch arabinogalactan, corn fiber arabinoxylan, and tamarind seed xyloglucan, with terminal galactose contents varying from 6% to 40%. A multienzyme system was used, with catalase and horseradish peroxidase to enhance the action of galactose oxidase. An analysis technique was developed for the quantification of the reactive aldehydes with GC-MS, utilizing NaBD4 reduction and acidic methanolysis. The best oxidation degrees of terminal galactosyls were obtained with xyloglucan (85% of galactose) and spruce galactoglucomannan (65% of galactose). The highest oxidation degree based on total carbohydrates was achieved with guar gum (28%), which had the highest galactose content. The oxidation resulted in changes in the physicochemical properties of the polysaccharide solutions, and the changes observed varied between the polysaccharides. The clearest change was in tamarind xyloglucan, which formed a gel after the oxidation. After the oxidation, larger particles were present in the solution of spruce galactoglucomannan, but changes in its rheological properties were not observed.