ethyl 2,3,4-tri-O-acetyl-1-thio-β-L-rhamnopyranoside | 69558-02-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 2,3,4-tri-O-acetyl-1-thio-β-L-rhamnopyranoside
• 英文别名: Ethyl 2,3,4-tri-O-acetyl-1-thio-beta-L-rhamnopyranoside；[(2S,3S,4R,5R,6R)-4,5-diacetyloxy-6-ethylsulfanyl-2-methyloxan-3-yl] acetate
• CAS: 69558-02-7
• 化学式: C₁₄H₂₂O₇S
• 分子量: 334.39
• InChiKey: BSQTXTAGEJNXTK-DRIGJWAJSA-N

物化性质

• 熔点：
  156-159 °C
• 沸点：
  391.3±42.0 °C(Predicted)
• 密度：
  1.22±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  22
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.79
• 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：

  ethyl 2,3,4-tri-O-acetyl-1-thio-β-L-rhamnopyranoside 在 4 A molecular sieve 、 sodium methylate 、 三氟甲烷磺酸甲酯 作用下， 以 甲醇 、 乙醚 为溶剂， 反应 42.5h， 生成 methyl 2-acetamido-6-O-benzyl-2-deoxy-3-O-(β-D-galactopyranosyl)-4-O-(α-L-rhamnopyranosyl)-β-D-glucopyranoside
  参考文献：
  名称：

  The Amide Group in N-Acetylglucosamine Glycosyl Acceptors Affects Glycosylation Outcome

  摘要：

  Glycosylation of a disaccharide containing N-acetylglucosamine with rhamnosyl and mannosyl trichloracetimidates under triethysilyl triflate catalysis led to the competitive formation of glycosyl imidates. While the rhamnosyl imidate could be rearranged to the thermodynamically favored trisaccharide, the mannosyl analogue was resistant to rearrangement. Glycosylation with perbenzylated thiorhamnosides activated with methyl triflate (MeOTf) gave the trisaccharide as well as the methyl imidate trisaccharide. The less reactive alpha-thioethyl donor led to a higher relative amount of methyl imidate trisaccharide to trisaccharide than the more reactive beta-thioglycoside. When using a more reactive thioethyl fucoside only the trisaccharide was obtained. Interestingly, the acceptor treated with MeOTf gave the N-methyl imidate that could be easily rhamnosylated and subsequently converted to the N-acetamido trisaccharide. This strategy to glycosylate O-4 of N-acetylglucosamine is under further investigation. Alternatively, bis-N-acetylation of the glucosamine prevented the formation of imidates and allowed the efficient synthesis of two Lewis A trisaccharide analogues.

  DOI：

  10.1021/jo050707+
• 作为产物：
  描述：

  L-rhamnopyranose 在 4-二甲氨基吡啶 、 三氟化硼乙醚 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 1.83h， 生成 ethyl 2,3,4-tri-O-acetyl-1-thio-β-L-rhamnopyranoside 、 乙基 2,3,4-三-O-乙酰基-6-脱氧-1-硫代-alpha-L-吡喃甘露糖苷
  参考文献：
  名称：

  用于制备均质糖偶联疫苗候选物的协调合成和偶联策略

  摘要：

  一个甜蜜的解决方案：提出了一种合成明确定义的基于碳水化合物的疫苗的策略。该方法将复杂的寡糖合成与位点特异性结合方法相结合，以提供纯糖蛋白候选疫苗（见方案）。

  DOI：

  10.1002/anie.201006327

文献信息

• A stereospecific approach towards the synthesis of 2-deoxy α- and β-glycosides based on a 1,2-ethyl (phenyl) thio group migration
  作者：H.M. Zuurmond、P.A.M. van der Klein、G.A. van der Marel、J.H. van Boom

  DOI：10.1016/s0040-4020(01)80165-4

  日期：1993.1

  Iodonium ion (NIS/TfOH)-assisted glycosylation of a sugar acceptor with properly protected ethyl (phenyl) 2-O-phenoxythiocarbonyl 1-thio-β-D-gluco- or 1-thio-α-D-mannopyranoside donors gives the respective 1,2-trans linked 2′-ethyl (phenyl) thio-2′-deoxy-α-D-manno- or β-D-glucopyranosides.

  用适当保护的乙基（苯基）2 - O-苯氧基硫羰基1-硫-β-D-葡萄糖或1-硫代-α-D-甘露吡喃糖苷供体的碘受体的碘鎓离子（NIS / TfOH）辅助糖基化反应分别给出1,2-反式连接的2'-乙基（苯基）硫基-2'-脱氧-α-D-甘露糖苷或β-D-吡喃葡萄糖苷。
• Synthesis of Anomeric Sulfimides and Their Use as a New Family of Glycosyl Donors
  作者：Florence Chéry、Stéphanie Cassel、Hans Peter Wessel、Patrick Rollin

  DOI：10.1002/1099-0690(20021)2002:1<171::aid-ejoc171>3.0.co;2-7

  日期：2002.1

  We introduce a convenient synthesis of anomeric sulfimides, the ability of which to act as glycosyl donors has been tested with various thiophilic reagents and acceptors.

  我们介绍了一种方便的异头磺酰亚胺合成方法，其作为糖基供体的能力已经用各种亲硫试剂和受体进行了测试。
• Chemoenzymatic Synthesis of Naturally Occurring Benzyl 6-O-Glycosyl-.BETA.-D-glucopyranosides
  作者：Eiji Kawahara、Mikio Fujii、Keisuke Kato、Yoshiteru Ida、Hiroyuki Akita

  DOI：10.1248/cpb.53.1058

  日期：——

  Direct β-glucosidation between benzyl alcohol and D-glucose (5) using the immobilized β-glucosidase from almonds with the synthetic prepolymer ENTP-4000 gave a benzyl β-D-glucoside (1) in 53% yield. The coupling of the benzyl β-D-glucopyranoside congener (8) derived from 1 with phenyl 2,3,4-tri-O-acetyl-1-thio-β-D-xylopyranoside (9), ethyl 2,3,4-tri-O-acetyl-1-thio-α-L-rhamnopyranoside (13), and 2,3,4-tri-O-acetyl-α-L-arabinopyranosyl bromide (15) afforded 10, 14, and 16, respectively, as coupled products. Deprotection of 10, 14, and 16 provided the synthetic benzyl β-D-xylopyranosyl-(1→6)-β-D-glucopyranoside (2), benzyl α-L-rhamnopyranosyl-(1→6)-β-D-glucopyranoside (3), and benzyl α-L-arabinopyranosyl-(1→6)-β-D-glucopyranoside (4), respectively.

  使用来自杏仁的固定化β-葡萄糖苷酶，直接将苄醇与D-葡萄糖（5）进行β-葡萄糖苷化反应，获得了苄基β-D-葡萄糖苷（1），产率为53%。将来自1的苄基β-D-葡萄糖吡喃苷同系物（8）与苯基2,3,4-三-O-乙酰-1-硫-β-D-木糖吡喃苷（9）、乙基2,3,4-三-O-乙酰-1-硫-α-L-鼠李吡喃苷（13）和2,3,4-三-O-乙酰-α-L-阿拉伯吡喃糖基溴化物（15）进行偶联，分别获得了10、14和16作为偶联产物。对10、14和16进行去保护后，分别得到了合成的苄基β-D-木糖吡喃糖-(1→6)-β-D-葡萄糖吡喃苷（2）、苄基α-L-鼠李吡喃糖-(1→6)-β-D-葡萄糖吡喃苷（3）和苄基α-L-阿拉伯吡喃糖-(1→6)-β-D-葡萄糖吡喃苷（4）。
• The synthesis and biological evaluation of mycobacterial p-hydroxybenzoic acid derivatives (p-HBADs)
  作者：Jean Bourke、Corinna F. Brereton、Stephen V. Gordon、Ed C. Lavelle、Eoin M. Scanlan

  DOI：10.1039/c3ob42277a

  日期：——

  Synthetic p-hydroxybenzoic acid derivatives (p-HBADs) from Mycobacterium tuberculosis have the ability to suppress host immune response in vitro.

  合成的对羟基苯甲酸衍生物（p-HBADs）来自结核分枝杆菌，具有抑制宿主免疫反应的能力体外。
• An improved method for the preparation of some ethyl 1-thioglycosides
  作者：Saibal Kumar Das、Nirmolendu Roy

  DOI：10.1016/s0008-6215(96)00235-2

  日期：1996.12

  Abstract Ethyl 1-thioglycosides were prepared in almost quantitative yield from sugar peracetates in 3:2 chloroform-ether, with boron trifluoride diethyl etherate as catalyst. d -Galactose, d -glucose, and 2-deoxy-2-phthalimido- d -glucose yielded almost exclusively β anomers, whereas l -rhamnose and d -mannose resulted predominantly in the α anomers.

  摘要以三氟化硼二乙基醚化物为催化剂，由过乙酸糖在3：2的氯仿-乙醚中以几乎定量的产率制备了1-硫代糖苷。d-半乳糖，d-葡萄糖和2-脱氧-2-邻苯二甲酰亚胺基-d-葡萄糖几乎只产生β端基异构体，而1-鼠李糖和d-甘露糖主要产生α端基异构体。