2,6-脱水-5-脱氧-1,4-二-O-(三异丙基硅烷基)-D-阿拉伯糖-己-5-烯糖 | 201053-37-4

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 中文名称: 2,6-脱水-5-脱氧-1,4-二-O-(三异丙基硅烷基)-D-阿拉伯糖-己-5-烯糖
• 中文别名: 3,6-二-O-(三异丙基硅基)-D-半乳醛；3,6-二-O-(三异丙基甲硅烷基)-D-半乳醛
• 英文名称: 3,6-di-O-(triisopropylsilyl)-D-galactal
• 英文别名: (2R,3S,4R)-4-tri(propan-2-yl)silyloxy-2-[tri(propan-2-yl)silyloxymethyl]-3,4-dihydro-2H-pyran-3-ol
• CAS: 201053-37-4
• 化学式: C₂₄H₅₀O₄Si₂
• 分子量: 458.83
• InChiKey: YDOYFAHLHUEGEN-WXFUMESZSA-N

物化性质

• 沸点：
  462.1±45.0 °C(Predicted)
• 密度：
  0.965 g/mL at 25 °C(lit.)
• 闪点：
  >230 °F
• 稳定性/保质期：
  常温常压下稳定，避免与酸和强氧化剂接触。

计算性质

• 辛醇/水分配系数(LogP)：
  7.01
• 重原子数：
  30
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  47.9
• 氢给体数：
  1
• 氢受体数：
  4

安全信息

• 储存条件：
  密封储存，存放在阴凉干燥的仓库中。冷藏温度应保持在-20℃。

反应信息

• 作为反应物：
  描述：

  2,6-脱水-5-脱氧-1,4-二-O-(三异丙基硅烷基)-D-阿拉伯糖-己-5-烯糖 在 吡啶 、 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 iodonium(di-γ-collidine) perchlorate 、 三氟甲烷磺酸甲酯 、 lithium hexamethyldisilazane 作用下， 以 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 8.0h， 生成 N-[(2S,3R,4R,5S,6R)-2-((2R,3R,4R)-4-Benzyloxy-2-benzyloxymethyl-3,4-dihydro-2H-pyran-3-yloxy)-5-hydroxy-4-triisopropylsilanyloxy-6-triisopropylsilanyloxymethyl-tetrahydro-pyran-3-yl]-benzenesulfonamide
  参考文献：
  名称：

  Synthesis of Asialo GM₁. New Insights in the Application of Sulfonamidoglycosylation in Oligosaccharide Assembly:  Subtle Proximity Effects in the Stereochemical Governance of Glycosidation

  摘要：

  The total synthesis of asialo GM(1) (1a) has been accomplished, Using related chemistry, the methyl glycoside of the asialo compound (1b) has also been synthesized. These kinds of compounds have been identified as potential ligands for bacterial and viral infection sites, A simpler structure, which hits also been identified for its infection attracting structure in the context of glycopeptides and glycolipids (methyl glycoside 2), has also been synthesized. The key common phase in the syntheses involves the sulfonamidoglycosidation reaction which is used to create a beta-linkage leading to a galNAc residue joined to the C-4 hydroxyl group of a galactose unit either as a monosaccharide (see compound 2) or as C-4' in the contest of a lactosyl moiety, During the course of these studies there was encountered an unusual "proximal hydroxyl" directing effect. Thus, when C-4 on the galactose ring of an azaglycosylating donor bears a free hydroxyl (see, for instance, compound 13), beta-glycoside formation predominates. When this hydroxyl group is blocked, the process tends in the direction of alpha-glycoside formation (see compound 32), These findings were explained as arising from a critical intramolecular hydrogen bond between the C-4 axial hydroxyl of the galactose donor and its proximal pyranosidal ring oxygen. This interaction stabilizes conformations from which beta-glycosidation predominates.

  DOI：

  10.1021/ja9724957
• 作为产物：
  描述：

  (2R,3R,4R)-2-(羟基甲基)-3,4-二氢-2H-吡喃-3,4-二醇 在 咪唑 、 米帕明 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 2,6-脱水-5-脱氧-1,4-二-O-(三异丙基硅烷基)-D-阿拉伯糖-己-5-烯糖
  参考文献：
  名称：

  Synthesis of Asialo GM₁. New Insights in the Application of Sulfonamidoglycosylation in Oligosaccharide Assembly:  Subtle Proximity Effects in the Stereochemical Governance of Glycosidation

  摘要：

  The total synthesis of asialo GM(1) (1a) has been accomplished, Using related chemistry, the methyl glycoside of the asialo compound (1b) has also been synthesized. These kinds of compounds have been identified as potential ligands for bacterial and viral infection sites, A simpler structure, which hits also been identified for its infection attracting structure in the context of glycopeptides and glycolipids (methyl glycoside 2), has also been synthesized. The key common phase in the syntheses involves the sulfonamidoglycosidation reaction which is used to create a beta-linkage leading to a galNAc residue joined to the C-4 hydroxyl group of a galactose unit either as a monosaccharide (see compound 2) or as C-4' in the contest of a lactosyl moiety, During the course of these studies there was encountered an unusual "proximal hydroxyl" directing effect. Thus, when C-4 on the galactose ring of an azaglycosylating donor bears a free hydroxyl (see, for instance, compound 13), beta-glycoside formation predominates. When this hydroxyl group is blocked, the process tends in the direction of alpha-glycoside formation (see compound 32), These findings were explained as arising from a critical intramolecular hydrogen bond between the C-4 axial hydroxyl of the galactose donor and its proximal pyranosidal ring oxygen. This interaction stabilizes conformations from which beta-glycosidation predominates.

  DOI：

  10.1021/ja9724957

文献信息

• General Approach to Five-Membered Nitrogen Heteroaryl <i>C</i>-Glycosides Using a Palladium/Copper Cocatalyzed C–H Functionalization Strategy
  作者：Shuo Zhang、You-Hong Niu、Xin-Shan Ye

  DOI：10.1021/acs.orglett.7b01583

  日期：2017.7.7

  A general approach to the synthesis of diverse heteroaryl-C-Δ1,2-glycosides has been developed by employing the Pd(OAc)2/CuI cocatalyzed direct cross-coupling of five-membered nitrogen heterocycles with 1-iodoglycals in a C–H activation manner. Using this method, 27 examples of heteroaryl-C-Δ1,2-glycosides, containing indoles, thiazoles, benzothiazoles, imidazoles, benzimidazoles, and benzoxazoles

  到不同的杂芳基C-Δ的合成的一般方法1,2 -glycosides已经通过采用将Pd（OAC）开发2 /助催化的CuI直接的五元含氮杂环与1- iodoglycals在C-交叉偶联H激活方式。使用这种方法，杂芳基C-Δ的27个实例1,2 -glycosides，含有吲哚，噻唑，苯并噻唑，咪唑，苯并咪唑，苯并恶唑和在43-99％的产率获得的糖苷配基。
• β-Glycosyl Trifluoroborates as Precursors for Direct α-C-Glycosylation: Synthesis of 2-Deoxy-α-<i>C</i>-glycosides
  作者：Daiki Takeda、Makoto Yoritate、Hiroki Yasutomi、Suzuka Chiba、Takahiro Moriyama、Atsushi Yokoo、Kazuteru Usui、Go Hirai

  DOI：10.1021/acs.orglett.1c00402

  日期：2021.3.5

  C-Glycosides are metabolically stable mimics of natural O-glycosides and are expected to be useful tools for investigation of the biological functions of glycans. Here, we describe the synthesis of a series of aryl and vinyl C-glycosides by stereoinvertive sp3–sp2 cross-coupling reactions of 2-deoxyglycosyl boronic acid derivatives with aryl or vinyl halide, mediated by a photoredox/nickel dual catalytic

  C-糖苷是天然O-糖苷的代谢稳定模拟物，有望成为研究聚糖生物功能的有用工具。在这里，我们描述了通过2-脱氧糖基硼酸衍生物与芳基或乙烯基卤化物的立体反转 sp 3 -sp 2交叉偶联反应合成一系列芳基和乙烯基C-糖苷，由光氧化还原/镍双催化系统介导。乙烯基C-糖苷的氢化得到 C-连接的 2'-脱氧二糖类似物。
• Aziridine Ring Opening as Regio- and Stereoselective Access to C-Glycosyl-Aminoethyl Sulfide Derivatives
  作者：Aleksandra Tracz、Martyna Malinowska、Stanisław Leśniak、Anna Zawisza

  DOI：10.3390/molecules27061764

  日期：——

  A short synthetic route to stereoselective access to C-glycosyl-aminoethyl sulfide derivatives has been developed through the reaction of tributhyltin derivatives of glycals with aziridinecarboaldehyde and the regioselective ring opening of a chiral aziridine with thiophenol. The absolute configurations of the resulting diastereoisomers were determined by 1H NMR spectroscopy.

  通过甘醛的三丁锡衍生物与氮丙啶醛的反应以及手性氮丙啶与苯硫酚的区域选择性开环，开发了一种立体选择性获得C-糖基氨基乙基硫醚衍生物的短合成路线。所得非对映异构体的绝对构型通过 1 H NMR 光谱测定。
• Practical Synthesis of Spirocyclic Bis-C,C-glycosides. Mechanistic Models in Explanation of Rearrangement Stereoselectivity and the Bifurcation of Reaction Pathways
  作者：Leo A. Paquette、Margaret J. Kinney、Uta Dullweber

  DOI：10.1021/jo962020i

  日期：1997.3.1

  The susceptibility of glycal-derived carbinols to acid-catalyzed ring expansion is described. In the systems prepared from cyclopentanone, Ferrier ionization precedes the pinacol-like Wagner-Meerwein shift, thermodynamic control operates, and high stereoselectivity is seen if a C(6) substituent is present. In contrast, the adducts to cyclobutanone exhibit release of ring strain under kinetically controlled conditions and intercept the oxonium species reversibly formed via direct proton transfer. The results show that the substituents positioned on the glycal ring have a pronounced influence on whether a chair-like or twist-boat transition state geometry is adopted primarily. The composite reaction profiles reveal for the first time the fundamental importance of exothermicity and of substitution in these spiro glycosidation reactions. Since optical activity is preserved in all instances, the utility of this chemistry for the synthesis of bis-C,C-glycosides and more complex oxacyclics appears promising.
• Dubbaka, Srinivas Reddy; Steunenberg, Peter; Vogel, Pierre, Synlett, 2004, # 7, p. 1235 - 1238
  作者：Dubbaka, Srinivas Reddy、Steunenberg, Peter、Vogel, Pierre

  DOI：——

  日期：——