methyl α-D-glucuronide methyl ester | 18486-51-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl α-D-glucuronide methyl ester
• 英文别名: methyl (2S,3S,4S,5R,6S)-3,4,5-trihydroxy-6-methoxyoxane-2-carboxylate
• CAS: 18486-51-6
• 化学式: C₈H₁₄O₇
• 分子量: 222.195
• InChiKey: DCXMXXNUXSBWDI-XDUWNTRXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.5
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 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 α-D-glucuronide methyl ester 在 吡啶 、 甲醇 、 氨 、 一水合肼 作用下， 生成 1-O-methyl-α-D-glucopyranuronic acid hydrazide
  参考文献：
  名称：

  α-甲基-D-葡萄糖醛-吡喃糖苷衍生物的制备

  摘要：

  通过用四氧化二氮氧化α-甲基-葡萄糖-吡喃糖苷，我们首次成功地生产了纯结晶的α-甲基-葡萄糖醛酸-吡喃糖苷衍生物。

  DOI：

  10.1002/hlca.19490320642
• 作为产物：
  描述：

  alpha-甲基葡萄糖甙 在 盐酸 、 2,2,6,6-tetramethyl-piperidine-N-oxyl 、 Carbonate buffer 、 水 作用下， 以 甲醇 为溶剂， 反应 24.0h， 生成 methyl α-D-glucuronide methyl ester
  参考文献：
  名称：

  Electroorganic Synthesis 66: Selective Anodic Oxidation of Carbohydrates Mediated by TEMPO

  摘要：

  碳水化合物4-15在2,2,6,6-四甲基哌啶-1-氧自由基（TEMPO）的介导下进行阳极氧化。对初级羟基的选择性和完全反应在中等到优良的产率下生成相应的羧酸16-32。甲基α-d-葡萄糖苷以98%的产率转化为尿酸16。循环伏安法显示氧化是碱催化的，TEMPO+（2）对羟基的氧化是速率控制步骤。

  DOI：

  10.1055/s-1999-3464

文献信息

• Studies on the constituents of Momordica cochinchinensis Spreng. II. Isolation and characterization of the root saponins, Momordins I, II and III.
  作者：MASAYO IWAMOTO、HIKARU OKABE、TATSUO YAMAUCHI

  DOI：10.1248/cpb.33.1

  日期：——

  From the root of Momordica cochinchinensis SPRENG. (Cucurbitaceae), three saponins named momordins I, II and III have been isolated. Their structures were determined on the basis of chemical and spectral evidence as oleanolic acid 3-O-α-L-arabinopyranosyl (1→3)-β-D-glucuronopyranoside (momordin I), 28-O-β-D-glucopyranoside of momordin I (momordin II) and 3β-hydroxy-11α, 12α-epoxy-olean-28, 13-olide 3-O-α-L-arabinopyranosyl (1→3)-β-D-glucuronopyranoside (momordin III). Momordin II was proved to be identical with hemsloside Ma1 isolated from the tubers of Hemsleya macrosperma and H. chinensis.

  从木鳖子（Momordica cochinchinensis SPRENG. 葫芦科）的根中分离出三种皂苷，命名为木鳖子苷I、II和III。它们的结构通过化学和光谱证据确定为：木鳖子苷I（3-O-α-L-阿拉伯吡喃糖基（1→3）-β-D-葡萄糖醛酸苷基的齐墩果酸）、木鳖子苷II（木鳖子苷I的28-O-β-D-葡萄糖苷）和木鳖子苷III（3β-羟基-11α, 12α-环氧-齐墩果-28, 13-内酯的3-O-α-L-阿拉伯吡喃糖基（1→3）-β-D-葡萄糖醛酸苷）。木鳖子苷II被证实与从大苞赤瓟和中华赤瓟块根中分离出的hemsloside Ma1相同。
• Regioselective Carbohydrate Oxidations: A Nuclear Magnetic Resonance (NMR) Study on Selectivity, Rate, and Side-Product Formation
  作者：Niek N. H. M. Eisink、Martin D. Witte、Adriaan J. Minnaard

  DOI：10.1021/acscatal.6b03459

  日期：2017.2.3

  to palladium/neocuproine catalyzed oxidation and subsequently analyzed by qNMR. Surprisingly, all studied glucosides, mannosides, galactosides, and xylosides show selective oxidation of the C3-OH. However, subsequent reaction of the resulting ketone moiety is the main culprit for side product formation. Measures are reported to suppress these side reactions. The observed differences in reaction rate

  钯/新癸氨酸催化的糖苷氧化显示出对C3-OH的极佳选择性，但在甘露糖苷和半乳糖苷中，最初观察到非选择性氧化。为了进一步应用在更复杂的（低聚）糖中，就选择性和反应性而言，需要对反应有一个更好的了解。因此，合成了一组不同的糖苷，进行了钯/新星氨酸催化的氧化，随后通过qNMR进行了分析。出人意料的是，所有研究的糖苷，甘露糖苷，半乳​​糖苷和木糖苷均显示出对C3-OH的选择性氧化。然而，所得酮部分的后续反应是副产物形成的主要元凶。据报道，有措施抑制这些副反应。观察到的反应速率差异，葡萄糖苷氧化最快，
• Regioselective methylation of methyl glycopyranosides with diazomethane in the presence of transition-metal chlorides and of boric acid
  作者：Evgeny V. Evtushenko

  DOI：10.1016/s0008-6215(99)00044-0

  日期：1999.3

  Abstract Partial methylation of the methyl pyranosides of a number of pentoses, hexoses, 6-deoxyhexoses, methyl uronates and their methyl ethers with diazomethane in the presence of transition-metal chlorides and boric acid was studied. It was found for methyl glycosides of pentoses and 6-deoxyhexoses that tin(II), antimony(III), and titanium(IV) chlorides as well as boric acid promoted substitution

  摘要研究了在过渡金属氯化物和硼酸存在下，许多戊糖，己糖，6-脱氧己糖，尿酸甲酯及其甲基醚的甲基吡喃糖苷与重氮甲烷的部分甲基化。发现戊糖和6-脱氧己糖的甲基糖苷中锡（II），锑（III）和钛（IV）氯化物以及硼酸主要促进OH-3的取代，但被铈（III）和锌的取代（II）观察到盐主要取代了OH-2。在所有情况下，甲基β-1-鼠李糖吡喃糖苷的甲基化表现出较高的OH-2反应性。在氯化锡（II），锑（III）和铈（III）的存在下，己糖甲基糖苷的甲基化反应主要产生了3-甲基醚。不参与进一步络合的3-甲基醚 积聚高达50-80％的反应混合物（95％至100％的单甲醚馏分）。建议用于许多糖的方便的甲基醚的合成。
• [EN] 3'-KETOGLYCOSIDE COMPOUND FOR THE SLOW RELEASE OF A VOLATILE ALCOHOL<br/>[FR] COMPOSÉ 3'-CÉTOGLYCOSIDE POUR LA LIBÉRATION LENTE D'UN ALCOOL VOLATIL
  申请人：GLYCOSCIENCE S L

  公开号：WO2021160670A1

  公开（公告）日：2021-08-19

  The present invention relates to a 3'-ketoglycoside compound defined by formula (I) and its use for controlled release of alcohols, in particular alcohols showing an insect repellent effect. It relates also to a process for preparing the 3'-ketoglycoside compound of formula (I). It further relates to a composition comprising a 3'- ketoglycoside compound of formula (I). It relates also to the use of a 3'-ketoglycoside compound of formula (I) for the controlled release of alcohols. It related also to a method of use of such composition.

  本发明涉及由式(I)定义的3'-酮基糖苷化合物及其用于控制释放醇，特别是显示驱虫效果的醇。它还涉及制备式(I)的3'-酮基糖苷化合物的方法。此外，它还涉及包含式(I)的3'-酮基糖苷化合物的组合物。它还涉及使用式(I)的3'-酮基糖苷化合物来控制释放醇。它还涉及使用这种组合物的方法。
• Sigmatropic Rearrangement of Uronic Acid Derived Saccharide Allyl Ketene Acetals. A Study of Stereochemistry and Structural Limitations
  作者：Barbara Werschkun、Joachim Thiem

  DOI：10.1055/s-1999-3686

  日期：——

  Allyl ketene acetal Claisen rearrangement of urinoc acid derivatives with furanoside structure was studied. Reproducibility of the observed stereodiscrimination was confirmed in the conversion of enantiomeric starting materials. From X-ray structural data of the major reaction product obtained from a cis-pentenyl uronate, the transition state was proven to preferentially adopt a chair-like geometry. Alterations in the protecting group pattern led to a significant decrease in total yields. Use of β-deoxygenated starting material allowed a greater extent of variation, but was accompanied by the total loss of stereodiscrimination. For the first time, the reaction was applied to pyranoid starting material structures. The conversion of a gluco-configurated compound remaining unsuccessful, with the corresponding galacto and 4-deoxy derivatives an interesting stereoselectivity could be observed. This was lost by further structural simplification to a 1,4-dideoxypyranoid ring. This way, however, a substantial improvement in yield could be achieved.

  研究了具有呋喃糖苷结构的尿囊酸衍生物的烯丙基乙缩醛克莱森重排。在对映体起始材料的转化过程中，观察到的立体区分的可重复性得到了证实。从顺式戊烯基尿苷酸的主要反应产物的 X 射线结构数据来看，过渡态被证明优先采用椅子状几何结构。保护基团模式的改变导致总产率显著下降。使用δ-脱氧起始原料可以实现更大范围的变化，但同时也完全丧失了立体区分性。该反应首次应用于吡喃起始原料结构。葡萄糖构型化合物的转化仍未成功，但相应的半乳糖和 4-脱氧衍生物却出现了有趣的立体选择性。如果进一步将结构简化为 1,4-二脱氧吡喃环，这种立体选择性就会消失。不过，通过这种方法，可以大大提高产率。