methyl (methyl-2,3,4-tri-O-benzyl-α-D-glucopyranosid)uronate | 55610-71-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl (methyl-2,3,4-tri-O-benzyl-α-D-glucopyranosid)uronate
• 英文别名: methyl (2S,3S,4S,5R,6S)-3,4,5-tris(benzyloxy)-6-methoxytetrahydro-2H-pyran-2-carboxylate；methyl (2S,3S,4S,5R,6S)-6-methoxy-3,4,5-tris(phenylmethoxy)oxane-2-carboxylate
• CAS: 55610-71-4
• 化学式: C₂₉H₃₂O₇
• 分子量: 492.569
• InChiKey: ATDWPIKETLLHRS-AFBVCZJXSA-N

物化性质

• 沸点：
  586.3±50.0 °C(Predicted)
• 密度：
  1.21±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  36
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.34
• 拓扑面积：
  72.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl (methyl-2,3,4-tri-O-benzyl-α-D-glucopyranosid)uronate 在 氢氧化钾 、 水 作用下， 以 丙酮 为溶剂， 反应 1.0h， 以143 mg的产率得到methyl 2,3,4-tri-O-benzyl-α-D-glucuronic acid
  参考文献：
  名称：

  Synthesis and Reactions ofC-Hetaryl Substituted Ketoses

  摘要：

  O-Benzyl protected gluconolactone 1 reacts readily with 2-lithio derivatives of quinaldine, 2-methylquinoxaline, 2-methylbenzimidazole and N-protected derivatives, and 1-benzyloxymethyl-2-methylimidazole at low temperatures to afford as monoaddition products the corresponding D-gluco-2-heptuloses 2-5. The benzyl protective groups can be readily removed by hydrogenolysis as shown for the transformation of 4a into 8. Acylation reactions with 4a exhibited an interesting interplay between O- and N-acylation which is dependent on the nature of the acylating agent and on the reaction conditions. Reductive removal of the anomeric hydroxy group in 4a-c and 5 was readily performed via elimination products 18a-c and 23; their hydrogenation with Pd/C gave directly the O,N-deprotected C-beta-D-glucopyranosylmethyl derivatives 21 and 25, respectively.

  DOI：

  10.1080/07328309708006530
• 作为产物：
  描述：

  methyl 2,3,4-tri-O-benzyl-α-D-glucopyranuronate 在 silver perchlorate 、 三溴化磷 、 乙腈 作用下， 反应 0.67h， 生成 methyl (methyl-2,3,4-tri-O-benzyl-α-D-glucopyranosid)uronate
  参考文献：
  名称：

  Stereoselective glycosidations of uronic acids

  摘要：

  DOI：

  10.1016/s0040-4039(00)92735-7

文献信息

• The synthesis of glucosinolates deuterium labelled in the glucose fragment
  作者：Avril A. B. Robertson、Nigel P. Botting

  DOI：10.1002/jlcr.1141

  日期：2006.11

  A facile synthesis is described for 2,3,4,6-tetra-O-acetyl-thio-β-D- [1-H,6-H]glucopyranose, which has been used to make an isotopically labelled desulphoglucosinolate, [1′- H,6′-H]desulfogluconasturtiin. This isotopically labelled building block can be employed to make any glucosinolate or desulfoglucosinolate for use as internal standards for MS based analytical methods.

  描述了 2,3,4,6-四-O-乙酰基-硫代-β-D-[1-H,6-H] 吡喃葡萄糖的简便合成，该糖已用于制备同位素标记的脱硫代葡萄糖苷，[1 '- H,6'-H] 脱硫葡萄糖苷。这种同位素标记的构件可用于制备任何硫代葡萄糖苷或脱硫硫代葡萄糖苷，用作基于 MS 的分析方法的内标。
• Synthesis and Structural Analysis of Higher Analogs of Sucrose
  作者：Slawomir Jarosz、Mateusz Mach、Jadwiga Frelek

  DOI：10.1080/07328300008544111

  日期：2000.1

  Three sucrose monoalcohols with free hydroxyl groups at C-1', C-6, and C-6' (1, 4, and 6) were prepared selectively and in good yield from 2,3,3',4,4'-penta-O-benzylsucrose. These compounds were oxidized to aldehydes and reacted with stabilized ylide, Ph3P=CHCO2Me to afford appropriate α,β-unsaturated esters 10, 11, and 12. Each olefin was cis-hydroxylated with OsO4/NMO to stereoisomeric diols 13/14

  选择性地制备了三种在C-1'，C-6和C-6'（1、4和6）具有游离羟基的蔗糖一元醇，从2,3,3'，4,4'-五-O-苄基蔗糖。这些化合物被氧化成醛，并与稳定的叶立德（Ph 3 P = CHCO 2 Me）反应，得到适当的α，β-不饱和酯10、11和12。将每种烯烃用OsO 4 / NMO顺式羟基化为立体异构二醇13 / 14、15 / 16和17/18，其配置通过化学相关性和CD评估进行分配。osmylation反应的立体选择性极低（大约3：2），特别是与对6,7-不饱和甲基糖苷的简单衍生物进行的类似过程相比，其异构二醇的比例为10：1。11（在葡萄糖部分由C 2-单元同源的衍生物）的osmylation没有服从Kishi法则。蔗糖醛7与糖衍生的膦酸酯22的霍纳-埃蒙斯反应得到α，β-不饱和衍生物24，其在葡萄糖末端被C 7-单元同源。
• Phosphonate versus phosphorane method in the synthesis of higher carbon sugars. Preparation of D-erythro-L-manno-D-gluco-dodecitol
  作者：Sławomir Jarosz、Mateusz Mach

  DOI：10.1039/a807190j

  日期：——

  Higher sugar (C12 and C13) dialdose precursors 5, 10 and 15 were obtained by a coupling of C7-phosphorane 1 or C7-phosphonates 2 and 13 with C5- or C6-sugar aldehydes. These compounds were converted into higher dialdoses by (i) stereoselective reduction of a carbonyl group with zinc borohydride followed by (ii) osmylation of the resulting allylic alcohols. One of these derivatives – compound 8a – was

  通过使C 7-膦烷1或C 7-膦酸酯2和13与C 5-或C 6-糖醛偶合而获得高级糖（C 12和C 13）二糖前体5、10和15 。通过（i）用硼氢化锌立体选择性地还原羰基，然后（ii）将所得的烯丙基醇进行甲磺酰化，从而将这些化合物转化为更高的二元醇。一这些衍生物的-化合物8a -被转换成d -赤-大号-甘露- d -葡糖-dodecitol 23上0.5g的规模。
• A one-step C-linked disaccharide synthesis from carbohydrate allylsilanes and tri-O-acetyl-d-glucal
  作者：Anna de Raadt、Arnold E. Stütz

  DOI：10.1016/0008-6215(91)80009-c

  日期：1991.11

  The reaction of protected glucuronic esters 2 and 7, as well as D-glucuronolactone derivative 11, with (trimethylsilyl)methylmagnesium chloride in ether led to the corresponding stable bis-silyl adducts 3, 8, and 12, respectively. In Peterson-type reactions catalysed with mild acid, these compounds yielded carbohydrate allylsilanes 4, 9, and 13, respectively. Synthons 4 and 9 were coupled with tri-O-acetyl-D-glucal

  受保护的葡糖醛酸酯2和7，以及D-葡糖醛酸内酯衍生物11与（三甲基甲硅烷基）甲基氯化镁在醚中的反应分别产生相应的稳定的双甲硅烷基加合物3、8和12。在用弱酸催化的彼得森型反应中，这些化合物分别生成碳水化合物烯丙基硅烷4、9和13。在三氟化硼催化的“碳-铁重排”反应中，合成子4和9与三-O-乙酰基-D-葡糖醛偶联，分别得到C连接的二糖，即所谓的“ C-二糖” 16和17 ，以合理的收益率。借助NMR在这些偶联产物的2,3-不饱和环的C-糖基碳上的异头构型的结构分配
• An efficient and direct esterification of uronic acids using H2SO4-SiO2 at room temperature
  作者：Varsha Tiwari、Kaliyappan Murugan、Shahulhameed Sabiah、Jeyakumar Kandasamy

  DOI：10.1016/j.tetlet.2022.153852

  日期：2022.6

  A simple and convenient method for the esterification of various monosaccharide and disaccharide uronic acids, derived from glucose, galactose and mannose, was developed with different alcohols using the eco-friendly catalyst silica-sulphuric acid (H2SO4-SiO2). The esterification reactions proceeded at room temperature under mild conditions with excellent yields. Under the standard reaction conditions

  使用环保催化剂二氧化硅-硫酸（H 2 SO 4 -SiO 2），开发了一种简便的酯化方法，用于由葡萄糖、半乳糖和甘露糖衍生的各种单糖和二糖糖醛酸与不同醇的酯化反应。酯化反应在室温下温和条件下以优异的产率进行。在标准反应条件下，对乙酰基、苯甲酰基、新戊酰基、异亚丙基、苄基、萘基等各种敏感保护基团具有良好的耐受性。部分保护的糖醛酸在不发生自缩合反应的情况下进行酯化。