phenyl 2,3-di-O-acetyl-1-thio-β-D-galactopyranoside | 208644-68-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 2,3-di-O-acetyl-1-thio-β-D-galactopyranoside
• CAS: 208644-68-2
• 化学式: C₁₆H₂₀O₇S
• 分子量: 356.397
• InChiKey: KPMKSXYCBSBBDH-CWVYHPPDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.72
• 重原子数：
  24.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  102.29
• 氢给体数：
  2.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  phenyl 2,3-di-O-acetyl-1-thio-β-D-galactopyranoside 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 24.5h， 生成 Acetic acid (2S,3R,4S,5S,6R)-3-acetoxy-6-acetoxymethyl-5-phenoxythiocarbonyloxy-2-phenylsulfanyl-tetrahydro-pyran-4-yl ester
  参考文献：
  名称：

  从糖苷水解酶到硫糖寡糖：硫糖苷的合成

  摘要：

  用适当的糖基供体和糖苷水解酶或糖合酶处理各种含活性硫醇基的糖基受体，都不能产生任何硫糖苷，只能形成O-糖基化产物。然而，当使用硫代糖基寡糖酶来介导受体和供体之间的反应时，形成了硫代糖苷。实际上，在C3，C4或C6具有巯基的吡喃糖受体（但没有C2）均能够转化为硫糖苷。给出了有关各种过程机制的一些评论。

  DOI：

  10.1016/j.tetasy.2004.12.004
• 作为产物：
  描述：

  phenyl 2,3-di-O-acetyl-4,6-di-O-benzylidene-1-thio-β-D-galactopyranoside 在 camphor-10-sulfonic acid 、 2,2-二甲基-1,3-丙二醇 作用下， 以 二氯甲烷 为溶剂， 生成 phenyl 2,3-di-O-acetyl-1-thio-β-D-galactopyranoside
  参考文献：
  名称：

  4,6-O-[1-Cyano-2-(2-iodophenyl)ethylidene] Acetals. Improved Second-Generation Acetals for the Stereoselective Formation of β-d-Mannopyranosides and Regioselective Reductive Radical Fragmentation to β-d-Rhamnopyranosides. Scope and Limitations

  摘要：

  The [1-cyano-2-(2-iodophenyl)]ethylidene group is introduced as an acetal-protecting group for carbohydrate thioglycoside donors. The group is easily introduced under mild conditions, over short reaction times, and in the presence of a wide variety of other protecting groups by the reaction of the 4,6-diol with triethyl (2-iodophenyl)orthoacetate and camphorsulfonic acid, followed by trimethylsilyl cyanide and boron trifluoride etherate. The new protecting group conveys strong beta-selectivity with thiomannoside donors and undergoes a tin-mediated radical fragmentation to provide high yields of the synthetically challenging beta-rhamnopyranosides. The method is also applicable to the glucopyranosides when high beta-selectivity is observed in the coupling reaction and alpha-quinovosides are formed selectively in the radical fragmentation step. In the galactopyranoside series, beta-glycosides are formed selectively on coupling to donors protected by the new system, but the radical fragmentation is unselective and gives mixtures of the 4- and 6-deoxy products. Variable-temperature NMR studies for the glycosylation step, which helped define an optimal protocol, are described.

  DOI：

  10.1021/jo0526688

文献信息

• Regioselective monochloro substitution in carbohydrates and non-sugar alcohols via Mitsunobu reaction: applications in the synthesis of reboxetine
  作者：Abdul Rouf Dar、Mushtaq A. Aga、Brijesh Kumar、Syed Khalid Yousuf、Subhash Chandra Taneja

  DOI：10.1039/c3ob40853a

  日期：——

  A regioselective high yielding monochloro substitution (chlorohydrin formation) via Mitsunobu reaction is reported. In carbohydrates and sterically hindered non-sugars, only the primary hydroxyl group is chlorinated, whereas in the non-sugar 1,2- and 1,3-alcohols, predominantly the secondary chloride substitution occurs. The versatile methodology provides indirect access to epoxides with the retention

  据报道通过Mitsunobu反应的区域选择性高产一氯取代（氯醇形成）。在碳水化合物和受阻位的非糖中，仅伯羟基被氯化，而在非糖1,2-和1,3-醇中，主要发生仲氯取代。与常规的Mitsunobu反应可逆生成环氧化物的方法不同，通用的方法可在保留结构的情况下间接获得环氧化物。该方法已成功用作抗抑郁药光学活性非对映异构体合成的关键步骤瑞波西汀（R）-2，3- O-环己叉基-D-甘油醛的总产率为〜43％。
• Synthesis of 6′-galactosyllactose, a deviant human milk oligosaccharide, with the aid of <i>Candida antarctica</i> lipase-B
  作者：Kaarel Erik Hunt、Alfonso T. García-Sosa、Tatsiana Shalima、Uko Maran、Raivo Vilu、Tõnis Kanger

  DOI：10.1039/d2ob00550f

  日期：——

  and the sixth position deacetylation. While α-anomer of peracetylated D-galactose remained unreactive and β-anomer favoured the first position deacetylation. Peracetylated L-fucose, on the other hand, had no selectivity as the main product was fully unprotected L-fucose. Taking the peracetylated D-glucose deacetylation reaction product and selectively protecting the primary hydroxyl group in the sixth

  在过去十年中，对母乳低聚糖 (HMO) 的研究有所增加，对其有益效果表现出极大的兴趣。在这里，我们描述了一种使用固定化南极念珠菌脂肪酶-B、Novozyme N435 (N435) 对有机介质中的吡喃糖进行选择性脱乙酰化的方法，目的是简化和改进 HMO 的合成途径。通过首先深入研究过乙酰化D-葡萄糖的脱乙酰化反应，发现了两种反应条件，分别用于不同的 HMO 结构单元、过乙酰化糖和硫苷。基于D-葡萄糖的糖类对第四位和第六位脱乙酰化显示出选择性。而过乙酰化D的 α-异头物-半乳糖保持不反应并且β-异头物有利于第一位置的脱乙酰化。另一方面，过乙酰化L-岩藻糖没有选择性，因为主要产物是完全未受保护的L-岩藻糖。取过乙酰化的D-葡萄糖脱乙酰化反应产物并选择性地保护第六位的伯羟基，只留下第四位用于糖基化。同时，D-半乳糖硫苷的脱乙酰化产物，第六位脱乙酰化，同时具有受体和供体能力。使用源自 N435 脱乙酰化反应的上述两种产物，合成了异常的
• HClO4–silica-catalysed regioselective opening of benzylidene acetals and its application towards regioselective HO-4 glycosylation of benzylidene acetals in one-pot
  作者：Saidulu Dara、Varma Saikam、Mahipal Yadav、Parvinder Pal Singh、Ram A. Vishwakarma

  DOI：10.1016/j.carres.2014.01.011

  日期：2014.6

  Here we report a high-yielding method for the regioselective reductive ring opening of 4,6-O-benzylidene acetals of hexapyranosides using inexpensive and robust HClO4-SiO2 as the acidic catalyst and triethyl-silane as the hydride donor. Under the optimized condition, gluco-and mannopyranosides give the respective 6-O-benzyl derivative in good to excellent yields while the corresponding galactopyranoside gives the corresponding 6-O-benzyl derivative in lower yield. As the optimized condition involves acidic catalyst, we also successfully developed further application of the present method for the tandem regioselective opening and glycosylation in one-pot. (C) 2014 Elsevier Ltd. All rights reserved.
• Chemical Synthesis of (4,6-Pyr)-Gal β1→4GlcNAcβ1→3Fucβ1→OMe: A Pyruvated Trisaccharide Related to the Cell Aggregation of the Sponge<i>Microciona Prolifera</i>
  作者：Shaojiang Deng、Biao Yu、Zhongwu Guo、Yongzheng Hui

  DOI：10.1080/07328309808002904

  日期：1998.4

  4,6-O-[(R)-1-carboxylethylidene] Gal beta 1-->4GlcNAc beta 1-->3Fuc beta 1-->OMe, a pyruvated trisaccharide unit involved in the aggregation factor of the marine sponge Microciona prolifera, was synthesized stereospecifically and unambiguously employing thioglycosides as glycosyl donors to construct glycosidic bonds.