methyl 2,3-O-methyl-4,6-O-carbonyl-α-D-glucopyranoside | 29085-82-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: methyl 2,3-O-methyl-4,6-O-carbonyl-α-D-glucopyranoside
• 英文别名: (4aR,6S,7R,8S,8aR)-6,7,8-trimethoxy-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-2-one
• CAS: 29085-82-3
• 化学式: C₁₀H₁₆O₇
• 分子量: 248.233
• InChiKey: ATKTXYMVFVZJAP-ZEBDFXRSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.9
• 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 2,3-O-methyl-4,6-O-carbonyl-α-D-glucopyranoside 、 (4-甲基苯基)甲醇 在 1,5,7-三氮杂双环[4.4.0]癸-5-烯 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 生成 、 、 、
  参考文献：
  名称：

  在葡萄糖碳酸酯的开环聚合过程中调用侧链功能来调节区域选择性

  摘要：

  在 1,5,7-三氮杂双环 [5.4.0]dec-5-烯 (TBD) 有机碱催化的六元环状 d-葡萄糖开环聚合 (ROP) 中侧链官能团的参与程度-发现基碳酸盐导致显着不同的区域化学结果。对于在 2 位和 3 位含有碳酸酯侧链取代基的天然衍生聚（4,6-d-葡萄糖碳酸酯）（PGC），观察到高区域选择性，而在具有醚侧链取代基的类似 PGC 中发现了区域不规则性。这些 PGC 的骨架连接性和结构细节通过对单聚体和二聚体的综合 1D 和 2D NMR 研究的组合进行检查，验证开环偏好并表明侧链功能在区域选择性 ROP 过程中的贡献。通过密度泛函理论计算证明了对侧链官能团奇怪作用的分子理解，揭示了侧链官能团与过渡态 TBD 之间的分子间氢键的稳定作用。总的来说，这项工作提供了对这些特定六元不对称环状葡萄糖碳酸酯的有机催化 ROP 的基本见解。更重要的是，这些发现为未来的设计策略奠定了基础，这些策略

  DOI：

  10.1021/jacs.0c05610
• 作为产物：
  描述：

  methyl 4-O-benzoyl-6-bromo-6-deoxy-2,3-di-O-methyl-α-D-glucopyranoside 在 二氧化碳 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 sodium hydroxide 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 20.0 ℃ 、1.0 MPa 条件下， 反应 7.0h， 生成 methyl 2,3-O-methyl-4,6-O-carbonyl-α-D-glucopyranoside
  参考文献：
  名称：

  具有线性和大环结构的，来自CO 2和糖苷的双环糖碳酸酯的疏水，亲水和两亲性聚糖碳酸酯

  摘要：

  两个双环glycocarbonates在从α甲基五步合成d葡糖苷不诉诸光气或它的衍生物的第一次。使用CO 2修饰葡萄糖的4位和6位以引入六元碳环作为羰基化试剂；首先将同一葡糖苷底物的2位和3位转化为甲基或三甘醇单甲醚基团，以保护这些位置免受不良反应的影响，并且在第一种情况下赋予疏水性，在第二种情况下赋予亲水性。然后在不同条件下研究了这些双环碳酸酯的聚合行为。一方面，通过上述单体的开环聚合，由p引发的线性聚碳酸碳酸酯均聚物和二嵌段共聚物被获得。-甲基苄醇，使用1,5,7-三氮杂双环[4.4.0] dec-5-ene（TBD）作为催化剂；另一方面，使用作为两性离子引发剂的1,8-二氮杂双环[5.4.0]十一碳-7-烯（DBU）来生长大环聚碳酸酯碳酸酯均聚物和二嵌段共聚物。通过NMR，GPC和MALDI-tof对衍生的各种结构进行了全面表征，并显示出预期的结构。最后，研究了线性和大环两亲共聚碳酸

  DOI：

  10.1021/acs.macromol.6b02527

文献信息

• Poly(<scp>d</scp>-glucose carbonate) Block Copolymers: A Platform for Natural Product-Based Nanomaterials with Solvothermatic Characteristics
  作者：Tiffany P. Gustafson、Alexander T. Lonnecker、Gyu Seong Heo、Shiyi Zhang、Andrew P. Dove、Karen L. Wooley

  DOI：10.1021/bm4010832

  日期：2013.9.9

  A natural product-based polymer platform, having the characteristics of being derived from renewable materials and capable of breaking down, ultimately, into natural byproducts, has been prepared through the ring-opening polymerization (ROP) of a glucose-based bicyclic carbonate monomer. ROP was carried out via chain extension of a polyphosphoester (PPE) macroinitiator in the presence of 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) organocatalyst to afford the PPE-b-poly(n-glucose carbonate) (PDGC) block copolymer. This new copolymer represents a functional architecture that can be rapidly transformed through thiol-yne reactions along the PPE segment into a diverse variety of amphiphilic polymers, which interestingly display stimuli-sensitive phase behavior in the form of a lower critical solution temperature (LCST). Below the LCST, they undergo self-assembly to form spherical core-shell nanostructures that display a poorly defined core-shell morphology. It is expected that hydrophobic patches are exposed within the micellar corona, reminiscent of the surface complexity of proteins, making these materials of interest for triggered and reversible assembly disassembly processes.
• Polycarbonates Derived from Glucose via an Organocatalytic Approach
  作者：Koichiro Mikami、Alexander T. Lonnecker、Tiffany P. Gustafson、Nathanael F. Zinnel、Pei-Jing Pai、David H. Russell、Karen L. Wooley

  DOI：10.1021/ja402319m

  日期：2013.5.8

  An organocatalyzed ring-opening polymerization methodology was developed for the preparation of polycarbonates derived from glucose as a natural product starting material. The cyclic 4,6-carbonate monomer of glucose having the 1, 2, and 3 positions methyl-protected was prepared in three steps from a commercially available glucose derivative, and the structure was confirmed by means of NMR and IR spectroscopies, electrospray ionization mass spectrometry (MS), and single-crystal Xray analysis. Polymerization of the monomer, initiated by 4-methylbenzyl alcohol in the presence of 1,5,7-triazabicyclo[4.4.0]dec-5-ene as the organocatalyst, proceeded effectively in a controlled fashion to afford the polycarbonate with a tunable degree of polymerization, narrow molecular weight distribution, and well-defined end groups, as confirmed by a combination of NMR spectroscopy, gel-permeation chromatography, and MALDI-TOF MS. A distribution of head-to-head, head-to-tail, and tail-to-tail regiochemistries was determined by NMR spectroscopy and tandem MS analysis by electron transfer dissociation. These polycarbonates are of interest as engineering materials because of their origination from renewable resources combined with their amorphous character and relatively high glass transition temperatures as determined by X-ray diffraction and differential scanning calorimetry studies.
• Hydrophobic, Hydrophilic, and Amphiphilic Polyglycocarbonates with Linear and Macrocyclic Architectures from Bicyclic Glycocarbonates Derived from CO₂ and Glucoside
  作者：Debasis Pati、Xiaoshuang Feng、Nikos Hadjichristidis、Yves Gnanou

  DOI：10.1021/acs.macromol.6b02527

  日期：2017.2.28

  other hand, macrocyclic polyglycocarbonate homopolymers and diblock copolymers were grown using 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) which served as zwitterionic initiator. The various architectures derived were all thoroughly characterized by NMR, GPC, and MALDI-tof and shown to exhibit the expected structure. Finally, the self-assembly of linear and macrocyclic amphiphilic copolyglycocarbonates

  两个双环glycocarbonates在从α甲基五步合成d葡糖苷不诉诸光气或它的衍生物的第一次。使用CO 2修饰葡萄糖的4位和6位以引入六元碳环作为羰基化试剂；首先将同一葡糖苷底物的2位和3位转化为甲基或三甘醇单甲醚基团，以保护这些位置免受不良反应的影响，并且在第一种情况下赋予疏水性，在第二种情况下赋予亲水性。然后在不同条件下研究了这些双环碳酸酯的聚合行为。一方面，通过上述单体的开环聚合，由p引发的线性聚碳酸碳酸酯均聚物和二嵌段共聚物被获得。-甲基苄醇，使用1,5,7-三氮杂双环[4.4.0] dec-5-ene（TBD）作为催化剂；另一方面，使用作为两性离子引发剂的1,8-二氮杂双环[5.4.0]十一碳-7-烯（DBU）来生长大环聚碳酸酯碳酸酯均聚物和二嵌段共聚物。通过NMR，GPC和MALDI-tof对衍生的各种结构进行了全面表征，并显示出预期的结构。最后，研究了线性和大环两亲共聚碳酸
• Invoking Side-Chain Functionality for the Mediation of Regioselectivity during Ring-Opening Polymerization of Glucose Carbonates
  作者：Yue Song、Xin Yang、Yidan Shen、Mei Dong、Yen-Nan Lin、Michael B. Hall、Karen L. Wooley

  DOI：10.1021/jacs.0c05610

  日期：2020.10.7

  side-chain functionalities during the 1,5,7-triazabicyclo[5.4.0]dec-5-ene (TBD) organobase-catalyzed ring-opening polymerizations (ROP) of six-membered cyclic d-glucose-based carbonates was found to result in significantly different regiochemical outcomes. High regioselectivity was observed for naturally derived poly(4,6-d-glucose carbonate)s (PGCs) containing carbonate side chain substituents in the 2- and

  在 1,5,7-三氮杂双环 [5.4.0]dec-5-烯 (TBD) 有机碱催化的六元环状 d-葡萄糖开环聚合 (ROP) 中侧链官能团的参与程度-发现基碳酸盐导致显着不同的区域化学结果。对于在 2 位和 3 位含有碳酸酯侧链取代基的天然衍生聚（4,6-d-葡萄糖碳酸酯）（PGC），观察到高区域选择性，而在具有醚侧链取代基的类似 PGC 中发现了区域不规则性。这些 PGC 的骨架连接性和结构细节通过对单聚体和二聚体的综合 1D 和 2D NMR 研究的组合进行检查，验证开环偏好并表明侧链功能在区域选择性 ROP 过程中的贡献。通过密度泛函理论计算证明了对侧链官能团奇怪作用的分子理解，揭示了侧链官能团与过渡态 TBD 之间的分子间氢键的稳定作用。总的来说，这项工作提供了对这些特定六元不对称环状葡萄糖碳酸酯的有机催化 ROP 的基本见解。更重要的是，这些发现为未来的设计策略奠定了基础，这些策略