O-(2,3,4,6-tetra-O-benzyl-β-D-galactopyranosyl)-cholesterol

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 类固醇和类固醇衍生物
• 英文名称: O-(2,3,4,6-tetra-O-benzyl-β-D-galactopyranosyl)-cholesterol
• 英文别名: O-[2,3,4,6-tetra-O-benzyl-β-D-galactopyranosyl]cholesterol；cholesteryl 2,3,4,6-tetra-O-benzyl β-D-galactopyranoside；cholesteryl 2,3,4,6-tetra-O-benzyl-β-D-galactopyranoside；cholesteryl 2,3,4,6-tetra-O-benzyl-D-β-galactopyranoside；cholesteryl 2,3,4,6-tetra-O-benzyl-D-galactopyranoside；(2R,3R,4S,5S,6R)-2-[[(3S,8S,9S,10R,13R,14S,17R)-10,13-dimethyl-17-[(2R)-6-methylheptan-2-yl]-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-yl]oxy]-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxane
• 化学式: C₆₁H₈₀O₆
• 分子量: 909.303
• InChiKey: DJWSRTRNMRPKQS-LCBFHFJCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  14.5
• 重原子数：
  67
• 可旋转键数：
  20
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  55.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  2,3,4,6-四-O-苄基-D-吡喃半乳糖 在 四溴化碳 、 三苯基膦 、 1,1,3,3-四甲基脲 作用下， 以 二氯甲烷 为溶剂， 反应 75.0h， 生成 O-(2,3,4,6-tetra-O-benzyl-β-D-galactopyranosyl)-cholesterol
  参考文献：
  名称：

  An easy access to halide ion-catalytic α-glycosylation using carbon tetrabromide and triphenylphosphine as multifunctional reagents

  摘要：

  2-O-苄基-1-羟基糖与CBr4和Ph3P反应生成一种即时的糖基溴化物，该溴化物在N,N-四甲基脲存在下与受体醇耦合，几乎定量地得到α-糖基产物。在提出的反应途径中，试剂组合扮演了多个角色，如糖基供体的生成、糖基化的活化以及反应体系的脱水作用。这些角色使得一个简单的α-糖基化反应得以进行，而无需特别关注脱水步骤。利用这种方法已经制备了多种α-糖基（D-葡萄糖、D-半乳糖和L-岩藻糖）产物，包括糖基甘油和胆固醇。

  DOI：

  10.1039/b303984f

文献信息

• An Air- and Water-Stable Iodonium Salt Promoter for Facile Thioglycoside Activation
  作者：An-Hsiang Adam Chu、Andrei Minciunescu、Vittorio Montanari、Krishna Kumar、Clay S. Bennett

  DOI：10.1021/ol5004059

  日期：2014.3.21

  iodonium salt phenyl(trifluoroethyl)iodonium triflimide is shown to activate thioglycosides for glycosylation at room temperature. Both armed and disarmed thioglycosides rapidly undergo glycosylation in 68–97% yield. The reaction conditions are mild and do not require strict exclusion of air and moisture. The operational simplicity of the method should allow experimentalists with a limited synthetic background

  空气和水稳定的碘鎓盐苯基（三氟乙基）碘鎓三氟甲磺酰亚胺在室温下可激活硫代糖苷以进行糖基化。武装和解除武装的硫糖苷都以 68-97% 的产率迅速进行糖基化。反应条件温和，不需要严格排除空气和水分。该方法的操作简单性应该允许具有有限合成背景的实验者构建糖苷键。
• Silicon Fluorides for Acid-Base Catalysis in Glycosidations
  作者：Amit Kumar、Yiqun Geng、Richard R. Schmidt

  DOI：10.1002/adsc.201100933

  日期：2012.5.21

  Adduct formation between alcohols as glycosyl acceptors and phenylsilicon trifluoride (PhSiF3) as catalyst permits acid‐base‐atalyzed glycosidations with O‐glycosyl trichloroacetimidates as glycosyl donors. In this way, from various glycosyl donors and acceptors 1,2‐trans‐ and some 1,2‐cis‐glycosides could be obtained with high anomeric selectivity. A preference for an intramolecular bimolecular nucleophilic

  醇（作为糖基受体）与苯基三氟化硅（PhSiF 3）作为催化剂之间的加合物形成允许酸碱催化的糖基化反应，其中O-糖基三氯乙酰胺酸作为糖基供体。这样，可以从各种糖基供体和受体以高异头异构体选择性获得1,2-反式和一些1,2-顺式-糖苷。结果显示，偏爱分子内双分子亲核取代（S N 2型）反应过程，伴有供体和受体激活。
• Glycosylation Reactions Using Phenyl(trifluoroethyl)iodonium Salts
  申请人：Trustees of Tufts College

  公开号：US20150099870A1

  公开（公告）日：2015-04-09

  Provided are methods for the preparation of glycosylation products, including those represented by formula I: Sugar-O—R′  I comprising the step of combining R′—OH, a glycosyl sulfide glycosyl donor (“thioglycoside donor”), a hypervalent iodine alkyl-transfer activating reagent, and a base. In an embodiment, the hypervalent iodine alkyl-transfer activating reagent is (phenyl(trifluoroethyl)iodonium triflimide).

  提供了制备糖基化产物的方法，包括由式I表示的那些： 糖-O—R′  I 包括将R′—OH、糖基硫醚糖基供体（“硫代糖苷供体”）、高价碘烷基转移活化试剂和碱结合的步骤。在一种实施例中，高价碘烷基转移活化试剂为（苯基(三氟乙基)碘三氟甲磺酰胺）。
• Substoichiometric FeCl3 Activation of Propargyl Glycosides for the Synthesis of Disaccharides and Glycoconjugates
  作者：Jianbo Zhang、Guosheng Sun、Yue Wu、Anqi Liu、Saifeng Qiu、Wan Zhang、Zhongfu Wang

  DOI：10.1055/s-0036-1591525

  日期：2018.3

  Glycosides as glycosyl donors using FeCl3 have been described. Under optimal reaction conditions, three kinds of propargyl glycosides were found to react with steroids and sugar-derived glycosyl acceptors to afford the corresponding disaccharides and glycoconjugates in good to excellent yields (66–91%). Meanwhile, the method can also realize one-pot synthesis of disaccharides, making it an effective

  已经描述了使用 FeCl3 作为糖基供体的糖苷。在最佳反应条件下，发现三种炔丙基糖苷与类固醇和糖衍生的糖基受体反应，以良好至极好的收率（66-91%）提供相应的二糖和糖缀合物。同时，该方法还可实现双糖的一锅法合成，是一种高效、经济、绿色的糖基化方法。
• Dehydrative Glycosylation with the Hendrickson Reagent
  作者：Matteo Mossotti、Luigi Panza

  DOI：10.1021/jo2015856

  日期：2011.11.4

  The Hendrickson reagent is able to perform efficiently dehydrative glycosylation of 1-hydroxyglycosyl donors. The reaction occurs under mild conditions through an anomeric oxophosphonium intermediate detected by nuclear magnetic resonance. Further insight into the mechanism was gained by 18O labeling of anomeric OH.

  亨德里克森试剂能够有效地进行1-羟基糖基供体的脱水糖基化。该反应在温和条件下通过核磁共振检测到的异头氧代intermediate中间体而发生。通过18 O标记异头OH获得了对该机理的进一步了解。