methyl β-D-[1-13C]glucopyranoside | 60821-15-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl β-D-[1-13C]glucopyranoside
• 英文别名: methyl [1-13C]-β-D-glucoside；Methyl beta-D-glucopyranoside-13C；(2R,3S,4S,5R,6R)-2-(hydroxymethyl)-6-methoxy(613C)oxane-3,4,5-triol
• CAS: 60821-15-0
• 化学式: C₇H₁₄O₆
• 分子量: 195.174
• InChiKey: HOVAGTYPODGVJG-XTARUXTJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -2.57
• 重原子数：
  13.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  99.38
• 氢给体数：
  4.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  methyl β-D-[1-13C]glucopyranoside 在 2,2,6,6-tetramethyl-piperidine-N-oxyl 、 次氯酸叔丁酯 作用下， 以 水 为溶剂， 以100%的产率得到methyl [1-13C]-β-D-glucuronide
  参考文献：
  名称：

  13C 交叉极化魔角旋转核磁共振光谱法测定膜转运蛋白的底物亲和力

  摘要：

  我们设计了方法，利用交叉极化魔角旋转 (CP-MAS) 固态核磁共振来测量 (13) C 标记的底物与膜转运蛋白结合的严格参数。这些方法适用于来自大肠杆菌的两种蛋白质：核苷转运蛋白 NupC 和葡萄糖苷酸转运蛋白 GusB。用含有低至 20 nmol 的 GusB 蛋白的样品实现了甲基 [1-(13) C]-β-d-葡糖苷酸与天然膜中过度表达的 GusB 结合的重要信号。拟合数据以产生 4.17 mM 的标记配体的 K(D) 值和 0.42 mM 的未标记配体对硝基苯基β-d-葡糖苷酸取代标记化合物的 K(D) 值。CP-MAS 还用于测量 [1'-(13)C] 尿苷与过表达的 NupC 的结合。含有[1'-(13)C] 尿苷的富含NupC 的膜的光谱展示了一个大峰，该峰来自底物绑定到除运输站点以外的未定义位点，这掩盖了来自底物绑定到NupC 的信号。在交叉极化/极化反转 (CPPI) NMR

  DOI：

  10.1021/ja037163i
• 作为产物：
  描述：

  1-(13)C-1,2,3,4,6-penta-O-acetylglucopyranose 在 calcium sulfate 、 氢溴酸 、 sodium methylate 、 乙酸酐 、 溶剂黄146 、 silver carbonate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 58.0h， 生成 methyl β-D-[1-13C]glucopyranoside
  参考文献：
  名称：

  13C 交叉极化魔角旋转核磁共振光谱法测定膜转运蛋白的底物亲和力

  摘要：

  我们设计了方法，利用交叉极化魔角旋转 (CP-MAS) 固态核磁共振来测量 (13) C 标记的底物与膜转运蛋白结合的严格参数。这些方法适用于来自大肠杆菌的两种蛋白质：核苷转运蛋白 NupC 和葡萄糖苷酸转运蛋白 GusB。用含有低至 20 nmol 的 GusB 蛋白的样品实现了甲基 [1-(13) C]-β-d-葡糖苷酸与天然膜中过度表达的 GusB 结合的重要信号。拟合数据以产生 4.17 mM 的标记配体的 K(D) 值和 0.42 mM 的未标记配体对硝基苯基β-d-葡糖苷酸取代标记化合物的 K(D) 值。CP-MAS 还用于测量 [1'-(13)C] 尿苷与过表达的 NupC 的结合。含有[1'-(13)C] 尿苷的富含NupC 的膜的光谱展示了一个大峰，该峰来自底物绑定到除运输站点以外的未定义位点，这掩盖了来自底物绑定到NupC 的信号。在交叉极化/极化反转 (CPPI) NMR

  DOI：

  10.1021/ja037163i

文献信息

• Gas-Phase Intercluster Thiyl-Radical Induced C–H Bond Homolysis Selectively Forms Sugar C2-Radical Cations of Methyl D-Glucopyranoside: Isotopic Labeling Studies and Cleavage Reactions
  作者：Sandra Osburn、Gaetano Speciale、Spencer J. Williams、Richard A. J. O’Hair

  DOI：10.1007/s13361-017-1667-2

  日期：2017.7.1

  exchangeable OH and NH protons with deuterons reveals that the sugar radical cation is formed in a process involving abstraction of a hydrogen atom from a C-H bond of the sugar coupled with proton transfer to the sugar, to form [M - H• + D+]. Investigation of this process using individual C-D labeled sugars reveals that the main site of H/D abstraction is the C2 position, since only the C2-deuterium

  一组甲基D-吡喃葡萄糖苷的同位素异构体与多级质谱实验结合使用，以确定通过最近开发的“生物启发”方法形成的糖自由基阳离子的自由基位点和裂解反应。在CID（MS2）的第一阶段，糖和S-亚硝基半胱胺[H3NCH2CH2SNO + M] +之间的质子化非共价复合物的碰撞诱导解离（CID）通过键均解释放硫代自由基，得到非共价自由基阳离子，[H3NCH2CH2S•+ M] +。该自由基阳离子复合物的CID（MS3）导致非共价复合物解离，生成糖自由基阳离子。用氘核取代所有可交换的OH和NH质子表明，糖自由基阳离子是在一个过程中形成的，该过程涉及从糖的CH键中夺取氢原子，然后将质子转移到糖中，从而形成[M-H•+ D +]。使用单个CD标记的糖对此过程进行的研究表明，H / D提取的主要位点是C2位置，因为只有C2氘标记的糖会产生占主导地位的[M-D•+ H +]产物离子。通过另一阶段的CID（MS4）研究了二糖糖基阳离子[M-H•+
• Synthesis of Methyl 4-O-methyl-β-D-ribo-hex-3-ulopyranoside-1-13C and Methyl 4-O-methyl-β-D-ribo-hex-3-ulopyranoside-3-13C as Fragment Analogues of Oxidized Cellulose Units
  作者：Karin Krainz、Andreas Hofinger、Thomas Dietz、Hans-Ulrich Suss、Antje Potthast、Thomas Rosenau

  DOI：10.2174/157017810791112478

  日期：2010.4.1

  Model compounds of oxidized anhydroglucose units in cellulosic materials, carrying 13C isotopic labels at specific positions, have been synthesized starting from commercially available 1-13C-D-glucose (14.7%) and 3-13C-Dglucose (6.3%), respectively, over 10 linear steps. To ensure high yields, the synthetic route was optimized with non-labeled material beforehand. The labeled compounds are used in studies of chromophore formation, yellowing, brightness reversion and aging of cellulosics.

  我们分别从市售的 1-13C-D 葡萄糖（14.7%）和 3-13C-D 葡萄糖（6.3%）开始，通过 10 个线性步骤合成了纤维素材料中氧化的脱氢葡萄糖单元的模型化合物，这些化合物在特定位置上带有 13C 同位素标记。为确保高产率，事先用非标记材料对合成路线进行了优化。标记化合物可用于纤维素的发色团形成、黄变、亮度还原和老化研究。
• Three-Bond C−O−C−C Spin-Coupling Constants in Carbohydrates:  Development of a Karplus Relationship
  作者：Bidisha Bose、Shikai Zhao、Roland Stenutz、Francis Cloran、Paul B. Bondo、Gail Bondo、Brian Hertz、Ian Carmichael、Anthony S. Serianni

  DOI：10.1021/ja981127f

  日期：1998.11.1

  A range of C-13-labeled carbohydrates containing C-O-C-C coupling pathways having different structures and dihedral angles has been prepared and used to identify structural factors affecting (3)J(COCC), especially those across the O-glycosidic Linkages of oligosaccharides. Model mono- and disaccharides were geometrically optimized using density functional methods, and scalar couplings involving carbon were calculated using a similar approach coupled with finite-field perturbation theory. Experimental and calculated (3)J(COCC) values were in close agreement, thus allowing use of the latter to better define the effect of carbohydrate structure on (3)J(COCC) magnitude. In addition to dihedral angle, the disposition of terminal electronegative substituents along the C-O-C-C coupling pathway significantly affects (3)J(COCC) values, and structural motifs have been identified where these effects may be encountered in oligosaccharides. A simple Karplus equation for trans-O-glycoside (3)J(COCC) values is proposed and has been applied in the reanalysis of trans-O-glycosidic couplings in C-13-labeled methyl beta-lactoside and sucrose. The behavior of trans-O-glycosidic (2)J(COC) and (3)J(COCH) values, which provide structural information complementary to that derived from (3)J(COCC) values, is also discussed.
• ⁴<i>J</i>_COCCH and ⁴<i>J</i>_CCCCH as Probes of Exocyclic Hydroxymethyl Group Conformation in Saccharides
  作者：Qingfeng Pan、Thomas Klepach、Ian Carmichael、Meredith Reed、Anthony S. Serianni

  DOI：10.1021/jo050615k

  日期：2005.9.1

  H-1 NMR spectra of aldohexopyranosyl rings containing C-13-enrichment at either C1 or C3 reveal the presence of long-range (4)J(C1),(H6R/s) and (4)J(C3),(H6R/S) whose magnitudes depend mainly on the O5-C5-C6-O6 torsion angle. Using theoretical calculations (density functional theory, DFT; B3LYP/ 6-31G*) and conformationally constrained experimental model compounds, the magnitudes and signs Of (4)J(C1,H6R/S) and (4)J(C3,H6R/S) have been established, and their dependencies on the geometry of the C1-O5-C5-C6-H6R/S and C3-C4-C5-C6-H6R/S coupling pathways, respectively, were determined. The latter dependencies mimic that observed previously for (4)J(HH) in aliphatic compounds such as propane. DFT calculations also showed that inclusion of non-Fermi contact terms is important for accurate predictions Of (4)J(CH) values. Application to methyl alpha- and beta-(D)-glucopyranosides reveals different rotameric distributions about their hydroxymethyl groups, with the beta-anomer enriched in the gt rotamer, in agreement with recent multi-J redundant coupling analyses. (4)J(C1,H6R/S) and (4)J(C3),(H6R/S) are expected to complement other recently developed J-couplings for the assignment of hydroxymethyl group conformation in oligosaccharides containing 1,6-glycosidic linkages.