methyl tetra-O-benzoyl-1-thio-β-D-glucopyranoside | 104707-00-8

• 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: methyl tetra-O-benzoyl-1-thio-β-D-glucopyranoside
• 英文别名: methyl 2,3,4,6-tetra-O-benzoyl-1-thio-β-D-glucopyranoside；[(2R,3R,4S,5R,6S)-3,4,5-tribenzoyloxy-6-methylsulfanyloxan-2-yl]methyl benzoate
• CAS: 104707-00-8
• 化学式: C₃₅H₃₀O₉S
• 分子量: 626.684
• InChiKey: JHMLQWPLDXTFRK-HOUGBNEZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.1
• 重原子数：
  45
• 可旋转键数：
  14
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  140
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  methyl tetra-O-benzoyl-1-thio-β-D-glucopyranoside 在 4 A molecular sieve 、 sodium methylate 、 苯基硒基三氟甲烷磺酸酯 作用下， 以 甲醇 、 1,2-二氯乙烷 为溶剂， 反应 2.17h， 生成 (3E)-4-[(4R)-4-(β-D-glucopyranosyloxy)-2,6,6-trimethyl-cyclohex-1-enyl]but-3-en-2-one
  参考文献：
  名称：

  Carotenoids and related polyenes. Part 9.1 Total synthesis of thermozeaxanthin and thermocryptoxanthin and the stabilizing effect of thermozeaxanthin on liposomes

  摘要：

  通过对 (3R)-3-hydroxy-β-ionone 7 的 β 选择性葡萄糖苷化，高效合成了热玉米黄质和热隐玉米黄质，并研究了玉米黄质 5、其葡萄糖苷 3 和热玉米黄质-15 1a 对脂质体的稳定作用。

  DOI：

  10.1039/b204011p
• 作为产物：
  描述：

  甲基-beta-D-硫代吡喃葡萄糖苷 生成 methyl tetra-O-benzoyl-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  A novel promoter for the efficient construction of 1,2-trans linkages in glycoside synthesis, using thioglycosides as glycosyl donors

  摘要：

  DOI：

  10.1016/s0008-6215(00)90385-9

文献信息

• Benzeneselenenyl triflate as a promoter of thioglycosides : A new method for O-glycosylation using thioglycosides
  作者：Yukishige Ito、Tomoya Ogawa

  DOI：10.1016/0040-4039(88)85335-8

  日期：1988.1

  An efficient O-glycosylation was developed by use of thioglycosides and benzeneselenenyl triflate.

  通过使用硫代糖苷和苯硒烯基三氟甲磺酸酯开发了有效的O-糖基化。
• Benzeneselenenyl triflate as an activator of thioglycosides for glycosylation reactions
  作者：Yukishige Ito、Tomoya Ogawa、Masaaki Numata、Mamoru Sugimoto

  DOI：10.1016/0008-6215(90)84078-9

  日期：1990.7

  A new method for the activation of thioglycosides was developed by use of benzeneselenenyl triflate (PhSeOTf), which, upon reaction with either a primary or secondary sugar HO-group, afforded O-glycosides under extremely mild reaction conditions. The reaction was applicable to various l-thiohexosides 2-6 as well as to a 2-thioglycoside 20 derived from N-acetylneuraminic acid (NeuAc).

  通过使用苯硒烯基三氟甲磺酸酯（PhSeOTf），开发了一种活化硫代糖苷的新方法，该方法与伯或仲糖HO-基团反应后，在极其温和的反应条件下提供了O-糖苷。该反应适用于各种1-硫代己糖苷2-6以及衍生自N-乙酰神经氨酸（NeuAc）的2-硫代糖苷20。
• Mild but Efficient Methods for Stereoselective Glycosylation with Thioglycosides: Activation by [<i>N</i>-Phenylselenophthalimide-Mg(ClO₄)₂] and [PhIO-Mg(ClO₄)₂]
  作者：Koichi Fukase、Yoshihiko Nakai、Takeshi Kanoh、Shoichi Kusumoto

  DOI：10.1055/s-1998-1575

  日期：1998.1

  Combinations of N-phenylselenophthalimide (N-PSP) or iodosobenzene (PhIO) with Mg(ClO4)2 effectively promote glycosylation with thioglycosides under mild conditions. A 2,2,2-trichloroethoxycarbonyl group or trityl protecting group at the 6-position increased α-selectivity on glycosylation with 2-O-benzylated donors.

  N-苯基硒苯肼酰胺（N-PSP）或碘苯（PhIO）与Mg(ClO4)2的组合有效促进了在温和条件下与硫糖苷的糖苷化反应。在6位引入2,2,2-三氯乙氧基羰基基团或三苯基保护基团可以提高与2-O-苄基供体的糖苷化反应中的α选择性。
• A New, Powerful Glycosylation Method:  Activation of Thioglycosides with Dimethyl Disulfide−Triflic Anhydride
  作者：János Tatai、Péter Fügedi

  DOI：10.1021/ol702139u

  日期：2007.10.1

  Dimethyl disulfide reacts with triflic anhydride to provide a highly reactive electrophile. Various thioglycosides, differing in their thio aglycons, carbohydrate units, and protecting group pattern, were activated with Me2S2-Tf2O in the presence of different glycosyl acceptors. The reactions proceeded at low temperatures within a short time, affording oligosaccharides in high yields both on primary

  二甲基二硫化物与三氟甲磺酸酐反应以提供高反应活性的亲电子试剂。在存在不同糖基受体的情况下，用Me2S2-Tf2O激活了各种硫代糖苷，它们的硫苷元，糖类单元和保护基团模式不同。反应在短时间内在低温下进行，伯羟基和仲羟基均以高收率得到寡糖。武装和解除武装的糖基供体被同样有效地激活。
• Investigation of the reactivity difference between thioglycoside donors with variant aglycon parts
  作者：Martina Lahmann、Stefan Oscarson

  DOI：10.1139/v02-101

  日期：2002.8.1

  The reactivity of perbenzoylated thioglycosides with various thiol aglycons has been compared and quantified using competitive glycosylation experiments. Methyl 2,3,4-tri-O-benzyl-α-D-glucopyranoside was employed as acceptor and DMTST as a promoter. The reactivity was found, as expected, to depend on the electron donating properties of the aglycon. Hence, the most reactive donor, the cyclohexyl thioglycoside, was found to be about three times as reactive as the thioethyl glycoside, which in turn was twice as reactive as the thiomethyl donor. The thiophenyl donor was even less reactive, whereas p-halophenyl donors were inert under the glycosylation conditions used — but could be activated using NIS–TfOH as promoter. Furthermore, it was found that galactosyl donors were three to four times more reactive than the corresponding glucosyl derivative. These results allowed the design of an orthogonal coupling between thioglycosides with the same protecting groups (benzoyls) but with different thiol aglycons. Key words: thioglycosides, orthogonal glycosylations, competititive glycosylations.

  已苯酰化硫代糖苷与不同硫醇配基的反应性进行了比较和定量化，使用竞争性糖基化实验。甲基2,3,4-三-O-苄基-α-D-葡萄糖吡喃糖苷被用作受体，DMTST被用作促进剂。如预期，发现反应性取决于硫配基的电子给予性质。因此，最具反应性的供体环己硫代糖苷发现比硫乙基糖苷反应性高约三倍，后者又比硫甲基供体反应性高出两倍。硫苯供体反应性更低，而对p-卤苯供体在糖基化条件下是惰性的，但可以使用NIS-TfOH作为促进剂激活。此外，发现半乳糖供体比相应的葡萄糖衍生物反应性高三到四倍。这些结果为设计具有相同保护基（苯酰基）但具有不同硫醇配基的硫代糖苷之间的正交偶联提供了可能。关键词：硫代糖苷，正交糖基化，竞争性糖基化。