phenyl 2,3,4-tri-O-acetyl-1-thio-β-L-arabinopyranoside | 98461-49-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: phenyl 2,3,4-tri-O-acetyl-1-thio-β-L-arabinopyranoside
• 英文别名: thiophenyl-2,3,4-O-triacetyl-L-arabinose；phenyl 2,3,4-tri-O-acetyl-1-thio-α-L-arabinopyranoside；phenyl 2,3,4-tri-O-acetyl-1-thio-L-arabinopyranoside；[(3S,4S,5R,6S)-4,5-diacetyloxy-6-phenylsulfanyloxan-3-yl] acetate
• CAS: 98461-49-5
• 化学式: C₁₇H₂₀O₇S
• 分子量: 368.408
• InChiKey: WUPNKWBRMZPWCP-NXOAAHMSSA-N

物化性质

• 沸点：
  451.0±45.0 °C(Predicted)
• 密度：
  1.29±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  25
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  113
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  phenyl 2,3,4-tri-O-acetyl-1-thio-β-L-arabinopyranoside 在 4-二甲氨基吡啶 、 4 A molecular sieve 、 Amberlite IR-118H 、 lutidine 、 camphor-10-sulfonic acid 、 三氟化硼乙醚 、 sodium methylate 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 34.0h， 生成 [(2S,3R,4S,5R)-2-[(2S,3R,4R,5S)-3-acetyloxy-2-phenylsulfanyl-5-triethylsilyloxyoxan-4-yl]oxy-4,5-bis[(4-methoxyphenyl)methoxy]oxan-3-yl] 4-methoxybenzoate
  参考文献：
  名称：

  抗癌天然产物 OSW-1 的全合成

  摘要：

  已从市售的 5-androsten-3beta-ol-17-one 79 中通过 10 次操作成功合成了高效的抗癌天然皂苷 OSW-1，总产率为 28%。全合成的关键步骤包括高度区域选择性和立体选择性二氧化硒介导的 80 烯丙基氧化和高度立体选择性 1,4-α-烷氧基乙烯基铜酸盐 68 加成到类固醇 17(20)-en-16-one 12E 引入类固醇侧链。这种全合成再次证明了我们实验室开发的 α-卤代乙烯基醚化学的多功能合成应用。

  DOI：

  10.1021/ja012119t
• 作为产物：
  描述：

  苯硫酚 在 sodium methylate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 1.83h， 生成 phenyl 2,3,4-tri-O-acetyl-1-thio-β-L-arabinopyranoside
  参考文献：
  名称：

  氯甲基糖苷作为制备糖基氧基甲基前药的通用合成子

  摘要：

  在药物分子上引入单糖以提高其溶解度、代谢稳定性和口服生物利用度。开发了一种新的氯甲基糖苷合成子，能够合成多种单糖前药。

  DOI：

  10.1002/chem.202103910

文献信息

• Dehydrative Thioglycosylation of 1-Hydroxyl Glycosides Catalyzed by In Situ-Generated AlI₃
  作者：Shiue-Shien Weng、Kun-Yi Hsieh、Zih-Jian Zeng

  DOI：10.1002/jccs.201600828

  日期：2017.5

  Thioglycosylation of 1‐hydroxyl glycosides catalyzed by in situ‐generated AlI3 from elemental aluminium and molecular iodine has been developed. This method provides an alternative route to access anomeric thioglycosides without the use of hazard Lewis acidic activators or per‐modified activated thiol sources. The major advantages of this dehydrative procedure are environmental friendly, ease of operation

  已经开发了由元素铝和分子碘原位生成的AlI 3催化的1-羟基糖苷的硫糖基化。该方法提供了另一种途径来使用异头硫醇苷，而无需使用危险的路易斯酸性活化剂或过修饰的活化硫醇源。该脱水步骤的主要优点是环境友好，操作简便，高异头非对映选择性和温和的反应条件。
• In(III) Triflate-Mediated Solvent-Free Synthesis and Activation of Thioglycosides by Ball Milling and Structural Analysis of Long Chain Alkyl Thioglycosides by TEM and Quantum Chemical Methods
  作者：Vajinder Kumar、Nikhil Taxak、Ramniwas Jangir、Prasad V. Bharatam、K. P. Ravindranathan Kartha

  DOI：10.1021/jo5001753

  日期：2014.4.18

  Conventional solution-phase synthesis of thioglycosides from glycosyl acetates and thiols in the presence of In(III) triflate as reported for benzyl thioglucoside failed when applied to the synthesis of phenolic and alkyl thioglycosides. But, it was achieved in high efficiency and diastereospecificity with ease by solvent-free grinding in a ball mill. The acetates in turn were also obtained by the homogenization of free sugars with stoichiometric amounts of acetic anhydride and catalytic In(OTf)(3) in the mill as neat products. Per-O-benzylated thioglycosides on grinding with an acceptor sugar in the presence of In(OTf)(3) yield the corresponding O-glycosides efficiently. The latter in the case of a difficult secondary alcohol was nearly exclusive (>98%) in 1,2-cis-selectivity. In contrast, the conventional methods for this purpose require use of a coreagent such as NIS along with the Lewis acid to help generate the electrophilic species that actually is responsible for the activation of the thioglycoside donor in situ. The distinctly different self-assembling features of the peracetylated octadecyl 1-thio-alpha-and beta-D-galactopyranosides observed by TEM could be rationalized by molecular modeling.
• Diastereoselective thioglycosylation of peracetylated glycosides catalyzed by in situ generated iron(III) iodide from elemental iodine and iron
  作者：Shiue-Shien Weng

  DOI：10.1016/j.tetlet.2009.07.077

  日期：2009.11

  A facile in situ preparation of Fe(III) iodide from cheap, abundant elemental iodine and iron metal served as an efficient catalyst for the thioglycosylation of peracetylated glycosides with various alkyl and aryl mercaptans. Due to neighboring participation, the anomerically pure beta-thioglycosides were obtained in good to high yields with exclusive diastereocontrol. (C) 2009 Published by Elsevier Ltd.
• Highly Diastereoselective Thioglycosylation of Functionalized Peracetylated Glycosides Catalyzed by MoO₂Cl₂
  作者：Shiue-Shien Weng、Yow-Dzer Lin、Chien-Tien Chen

  DOI：10.1021/ol062375g

  日期：2006.11.1

  Among 18 oxometallic species, MoO2Cl2 was found to be the most reactive in catalytic thioglycosylation of O-acetylated glycosides with functionalized thiols in CH2Cl2, leading cleanly to 1,2-trans-thioglycosides with exclusive diastereocontrol. The new catalytic protocol is applicable to a monoglycoside building block and beta-(1 -> 6)-S-linked-thiodisaccharide synthesis.
• Carbohydrate-Based NK1R Antagonists with Broad-Spectrum Anticancer Activity
  作者：Rocío Recio、Patricia Lerena、Esther Pozo、José Manuel Calderón-Montaño、Estefanía Burgos-Morón、Miguel López-Lázaro、Victoria Valdivia、Manuel Pernia Leal、Bernard Mouillac、Juan Ángel Organero、Noureddine Khiar、Inmaculada Fernández

  DOI：10.1021/acs.jmedchem.1c00793

  日期：2021.7.22