methyl α-D-gluco-hexodialdo-1,5-pyranoside | 23598-27-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl α-D-gluco-hexodialdo-1,5-pyranoside
• 英文别名: (2S,3S,4S,5R,6S)-3,4,5-Trihydroxy-6-methoxytetrahydro-2H-pyran-2-carbaldehyde；(2S,3S,4S,5R,6S)-3,4,5-trihydroxy-6-methoxyoxane-2-carbaldehyde
• CAS: 23598-27-8
• 化学式: C₇H₁₂O₆
• 分子量: 192.169
• InChiKey: HQELTDCENJWLGH-ZFYZTMLRSA-N

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-gluco-hexodialdo-1,5-pyranoside 在 sodium tetrahydroborate 、 盐酸 、 水 作用下， 以 水 为溶剂， 反应 1.0h， 生成 alpha-甲基葡萄糖甙
  参考文献：
  名称：

  Process for oxidizing primary alcohols

  摘要：

  在同时具有一次和二次羟基的底物中，可以通过在过氧硫酸盐存在下，使用环状亚硝基化合物接触底物，并在低于30℃和pH低于9的条件下进行反应，从而选择性地氧化一次羟基为醛基和/或羧基。该过程无卤素和无金属，特别适用于氧化多糖。

  公开号：

  US06936710B2
• 作为产物：
  描述：

  甲基 Β-D-吡喃葡萄糖苷 在 potassium permanganate 、 高氯酸 作用下， 生成 methyl α-D-gluco-hexodialdo-1,5-pyranoside
  参考文献：
  名称：

  Tribedi, Partha Sarathi, Journal of the Indian Chemical Society, 2001, vol. 78, # 6, p. 287 - 289

  摘要：

  DOI：

文献信息

• Oxidation of methyl and n-octyl α-d-glucopyranoside over graphite-supported platinum catalysts: effect of the alkyl substituent on activity and selectivity
  作者：Johannes H Vleeming、Ben F.M Kuster、Guy B Marin

  DOI：10.1016/s0008-6215(97)00157-2

  日期：1997.9

  catalyst was investigated. An increase of the length of the n-alkyl substituent from methyl to n-octyl resulted in a ten-fold decrease of the catalyst activity and an increase of the selectivity at pH 8.0 and 323 K. The selectivity decreased with increasing pH. The lower activity for a longer n-alkyl substituent is attributed to steric effects upon adsorption on the platinum surface and not to internal diffusion

  研究了在载有石墨的铂催化剂上用分子氧将甲基和正辛基Ol-D-吡喃葡萄糖苷氧化为甲基和正辛基Ce-D-glu-吡喃二葡萄糖苷。正烷基取代基的长度从甲基增加到正辛基导致催化剂活性降低十倍，并且在pH 8.0和323 K下的选择性增加。随着pH的增加，选择性降低。对于更长的正烷基取代基的较低活性归因于在铂表面上吸附时的空间效应，而不是由于内部扩散限制。提出了一个暂定的反应方案，该方案描述了通过仲羟基的氧化，环裂解和水解形成副产物的方法。主要副产品是具有2，4，4，4的一元羧酸盐和二元羧酸盐。烷基取代基的氧化产生6个碳原子和一元羧酸酯。CC-键裂解主要发生在2和C-3或C-4和C-5之间，前者对于较长的烷基取代基不太重要。对较长烷基取代基的较高选择性归因于其对水解的保护能力以及相邻羟基向铂表面的暴露。©1997爱思唯尔科学有限公司。
• Direct, Mild, and Selective Synthesis of Unprotected Dialdo-Glycosides
  作者：Marcus Angelin、Magnus Hermansson、Hai Dong、Olof Ramström

  DOI：10.1002/ejoc.200600288

  日期：2006.10

  A direct and highly convenient organocatalytic method for the preparation of 1,5-dialdo-pyranosides and 1,4-dialdo-furanosides is presented. The method relies on the chemoselective properties of TEMPO in combination with trichloroisocyanuric acid under very mild, basic conditions. Unprotected glycosides are prepared in a single step in high yields and are efficiently purified with the use of solid-phase

  提出了一种直接且高度方便的有机催化方法，用于制备 1,5-二醛基-吡喃糖苷和 1,4-二醛基-呋喃糖苷。该方法依赖于 TEMPO 与三氯异氰尿酸在非常温和的碱性条件下的化学选择性。未保护的糖苷以高产率一步制备，并使用固相亚胺捕获进行有效纯化。((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)。
• Process of oxidizing primary alcohols
  申请人：SCA Hygiene Products Zeist B.V.

  公开号：US06770755B1

  公开（公告）日：2004-08-03

  In a new process for oxidizing a primary and/or secondary alcohol, an oxidizing agent is used in the presence of a di-tertiary-alkyl nitroxyl, in an aqueous reaction medium at a pH of below 7. The di-tertiary-alkyl nitroxyl is especially 4-hydroxy-TEMPO, and the process is particularly advantageous for oxidizing carbohydrates such as starch.

  在一种新的氧化初级和/或次级醇的过程中，氧化剂在双三级烷基亚硝基的存在下，在pH低于7的水相反应介质中使用。双三级烷基亚硝基特别是4-羟基TEMPO，该过程特别有利于氧化淀粉等碳水化合物。
• Site‐ and Stereoselective Glycomodification of Biomolecules through Carbohydrate‐Promoted Pictet–Spengler Reaction
  作者：Bo Liu、Xiangman Zou、Yue Zhang、Yang Yang、Hao Xu、Feng Tang、Huixin Yu、Fei Xia、Zhi Liu、Jianwei Zhao、Wei Shi、Wei Huang

  DOI：10.1002/anie.202401394

  日期：2024.4.15

  biomolecules was developed using C6-oxidized glycans through a carbohydrate-promoted Pictet–Spengler reaction, providing homogeneous glycoconjugates with stable linkages. This method features high efficiency, mild conditions, robustness, biocompatibility, and applicability to a wide range of substrates, including glycans, peptides, proteins, and living-cell surfaces.

  通过碳水化合物促进的 Pictet-Spengler 反应，使用 C6 氧化聚糖开发了针对生物分子 N 末端色氨酸的糖修饰策略，提供具有稳定连接的均质糖缀合物。该方法具有效率高、条件温和、稳健、生物相容性以及适用于多种底物的特点，包括聚糖、肽、蛋白质和活细胞表面。
• Bromide-free TEMPO-mediated oxidation of primary alcohol groups in starch and methyl α-d-glucopyranoside
  作者：Petter L Bragd、Arie C Besemer、Herman van Bekkum

  DOI：10.1016/s0008-6215(00)00109-9

  日期：2000.9

  TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl)-mediated oxidation of potato starch and methyl a-D-glucopyranoside (MGP) was performed in the absence of sodium bromide (NaBr) as co-catalyst, solely using sodium hypochlorite (NaOCl) as the primary oxidant. The low reaction rate associated with a bromide-free process was increased by performing the oxidation at increased temperatures. The reaction proceeded stoichiometrically and with high selectivity and with only minor depolymerisation, provided that temperature and pH were kept 120 degrees C and < 9.0, respectively. At 20 degrees C and pH 8.5, the reaction rate was comparable to that of a corresponding oxidation catalysed by NaBr at 2 OC. Consequently, this is a simple approach to raise the TEMPO/NaOCl reaction rate under bromide-free conditions while still maintaining good product properties. At higher oxidation temperatures (greater than or equal to 25 degrees C) and under more alkaline conditions (pH greater than or equal to 9.0) degradation of the starch skeleton occurred. Simultaneously, side-reactions of the nitrosonium ion lowered the yield of the oxidation. Despite the absence of the NaBr catalyst, the reaction rate-controlling step was found to be the oxidation of the primary hydroxyl groups with the nitrosonium ion. The reaction was first-order in MGP and in TEMPO. (C) 2000 Elsevier Science Ltd. All rights reserved.