octa-O-acetyl-1-thio-α,β-trehalose | 65058-34-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: octa-O-acetyl-1-thio-α,β-trehalose
• 英文别名: (2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl)-2,3,4,6-tetra-O-acetyl-1-thio-β-D-glucopyranoside；(2,3,4,6-tetraacetoxy-α-D-glucosyl) 2,3,4,6-tetraacetoxy-1-S-β-D-glucoside；Bis-<2,2',3,3',4,4',6,6'-octa-O-acetyl-α,β'-D-glucopyranosyl>-sulfid；[(2R,3R,4S,5R,6S)-3,4,5-triacetyloxy-6-[(2R,3R,4S,5R,6R)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]sulfanyloxan-2-yl]methyl acetate
• CAS: 65058-34-6
• 化学式: C₂₈H₃₈O₁₈S
• 分子量: 694.665
• InChiKey: VJUMXLNMLSEYRN-HYSGBLIFSA-N

物化性质

• 熔点：
  170 °C
• 沸点：
  681.9±55.0 °C(Predicted)
• 密度：
  1.38±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  47
• 可旋转键数：
  20
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  254
• 氢给体数：
  0
• 氢受体数：
  19

反应信息

• 作为产物：
  描述：

  2,3,4,6-四乙酰氧基-alpha-D-吡喃葡萄糖溴化物 在 二硫化碳 、 sodiumsulfide nonahydrate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 0.08h， 以60%的产率得到octa-O-acetyl-1-thio-α,β-trehalose
  参考文献：
  名称：

  Stereoselective Synthesis of β-Glycosyl Thiols and Their Synthetic Applications

  摘要：

  A significantly fast reaction condition for the exclusive preparation beta-glycosyl thiol derivatives has been developed successfully. The reaction condition is one-step, fast, high yielding, highly stereoselective, and requires only benchtop chemicals. Further reaction of glycosyl thiol derivatives with Michael acceptors and alkylating agents furnished thioglycosides and (1,1)-thiolinked trehalose analogs.

  DOI：

  10.1021/jo302115k

文献信息

• Synthesis of <i>S</i>-Linked Glycoconjugates and <i>S</i>-Disaccharides by Thiol–Ene Coupling Reaction of Enoses
  作者：László Lázár、Magdolna Csávás、Mihály Herczeg、Pál Herczegh、Anikó Borbás

  DOI：10.1021/ol302098u

  日期：2012.9.7

  Free-radical hydrothiolation of the endocyclic double bond of enoses is reported. Reaction between 2-acetoxy-d-glucal and a range of thiols including amino acid, peptide, glycosyl thiols, and sugars with primary or secondary thiol functions gave S-linked α-glucoconjugates and S-disaccharides with full regio- and stereoselectivity. Addition of glycosyl thiols to a 2,3-unsaturated glycoside also proceeded

  报导了烯类的内环双键的自由基氢硫基化。之间的反应2-乙酰氧基- d -glucal和一系列硫醇，包括氨基酸，肽，糖基硫醇，和糖用伯或仲硫醇的功能都给小号-连接的α-glucoconjugates和小号具有完全区域选择性和立体选择性-disaccharides。糖基硫醇向2，3-不饱和糖苷的添加也以良好的选择性进行，并提供了一系列3-脱氧-S-二糖。
• Promotion of a Reaction by Cooling: Stereoselective 1,2‐<i>cis</i>‐α‐Thioglycoconjugation by Thiol‐Ene Coupling at −80 °C
  作者：Dániel Eszenyi、Viktor Kelemen、Fanny Balogh、Miklós Bege、Magdolna Csávás、Pál Herczegh、Anikó Borbás

  DOI：10.1002/chem.201800668

  日期：2018.3.26

  The photoinitiated thiol‐ene coupling reactions of 2‐substituted glycals were studied as a generally applicable strategy for stereoselective 1,2‐cis‐α‐thioconjugation. Although all glycals reacted with full α‐selectivity, the efficacy of the reactions varied in a broad range depending on their configuration and glycals bearing axial acetoxy substituents reacted with very low efficacy at room temperature

  研究了2-取代的糖的光引发硫醇-烯偶联反应，作为立体选择性的1,2-顺-α-硫缀合的普遍适用策略。尽管所有糖类均以完全的α-选择性反应，但反应的效率在很大程度上取决于其构型，带有轴向乙酰氧基取代基的糖类在室温下的反应效率很低。研究表明，冷却可促进反应进程，而加热则可抑制反应进程。在-80°C下，噻吩基向烯烃的快速可逆加成平衡几乎完全移向产物，从而导致有效的加成反应。通过利用这种独特的温度效应的一系列α硫代的升-fucosides， - d-半乳糖苷和d- GlcNAc衍生物的制备具有很高的功效和完全的立体选择性。
• Direct, stereoselective thioglycosylation enabled by an organophotoredox radical strategy
  作者：Peng Ji、Yueteng Zhang、Feng Gao、Fangchao Bi、Wei Wang

  DOI：10.1039/d0sc04136j

  日期：——

  transfer pathway have dictated glycosylation development, the direct glycosylation of readily accessible glycosyl donors as radical precursors is particularly appealing because of high radical anomeric selectivity and atom- and step-economy. However, the development of the radical process has been challenging owing to notorious competing reduction, elimination and/or SN side reactions of commonly used

  虽然涉及 2e -转移途径的策略决定了糖基化的发展，但由于自由基异头选择性高以及原子和步骤经济性，易于获得的糖基供体作为自由基前体的直接糖基化特别有吸引力。然而，由于常用的不稳定糖基供体的竞争性还原、消除和/或 S N副反应，自由基过程的发展一直充满挑战。在这里，我们介绍了一种有机光催化策略，通过光氧化还原介导的 HAT 催化，糖基溴可以有效地转化为相应的异头自由基，无需过渡金属或导向基团，并实现高度异头选择性。温和的反应条件能够合成具有挑战性的α-1,2-顺式硫代糖苷、各种官能团的耐受性以及常见戊糖和己糖的广泛底物范围，证明了该平台的强大功能。此外，这种通用方法与 sp 2和 sp 3硫亲电子试剂以及总共探测的 50 种底物的后期糖基多样化兼容。
• Hydrogen fluoride-mediated synthesis of 1-thiotrehaloses involving reaction of d-glucose with hydrogen sulfide
  作者：Jacques Defaye、Andrée Gadelle、Christian Pedersen

  DOI：10.1016/0008-6215(91)84116-v

  日期：1991.9

  Hydrogen sulfide reacted with D-glucose in hydrogen fluoride solution to yield preponderantly alpha,alpha-1-thiotrehalose, beta,beta-1-thiotrehalose, and the alpha,beta anomer. Conditions were found under which the thiotrehaloses were obtained in the respective proportions of 8:5:5.

  硫化氢与D-葡萄糖在氟化氢溶液中反应，主要生成α，α-1-硫代海藻糖，β，β-1-硫代海藻糖和α，β异头物。发现以8：5：5的相应比例获得硫代海藻糖的条件。
• GLYCOSYL DONOR, PREPARATION METHOD THEREFOR, AND USE THEREOF
  申请人：SICHUAN UNIVERSITY

  公开号：US20220127239A1

  公开（公告）日：2022-04-28

  A glycosyl donor represented by formula (I) is used for preparing an S-glycoside compound represented by formula (III), an O-glycoside compound represented by formula (V), and a C-glycoside compound represented by formula (V). The glycosyl donor is a raw material in the preparation of O-glycoside, S-glycoside, and C-glycoside compounds by means of a free radical reaction, most of which have a special α configuration.

  使用式(I)所代表的糖基供体，可用于制备式(III)所代表的S-糖苷化合物，式(V)所代表的O-糖苷化合物和式(V)所代表的C-糖苷化合物。该糖基供体是通过自由基反应制备O-糖苷化合物、S-糖苷化合物和C-糖苷化合物的原料之一，其中大部分具有特殊的α构型。