2-bromoethyl 1-deoxy-1-thio-2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside | 35927-64-1

• 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: 2-bromoethyl 1-deoxy-1-thio-2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside
• 英文别名: 2-bromoethyl 2,3,4,6-tetra-O-acetyl-1-thio-β-D-glucopyranoside；(2-bromo-ethyl)-(tetra-O-acetyl-1-thio-β-D-glucopyranoside)；(2-Brom-aethyl)-(tetra-O-acetyl-1-thio-β-D-glucopyranosid)；[(2R,3R,4S,5R,6S)-3,4,5-triacetyloxy-6-(2-bromoethylsulfanyl)oxan-2-yl]methyl acetate
• CAS: 35927-64-1
• 化学式: C₁₆H₂₃BrO₉S
• 分子量: 471.323
• InChiKey: ZISCOXPRDYJXQO-LJIZCISZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  27
• 可旋转键数：
  12
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  2-bromoethyl 1-deoxy-1-thio-2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside 在 sodium iodide 作用下， 以 甲醇 、 丙酮 为溶剂， 生成 (2R,3S,4S,5R,6S)-2-Hydroxymethyl-6-(2-methoxy-ethylsulfanyl)-tetrahydro-pyran-3,4,5-triol
  参考文献：
  名称：

  Preparation and Reactions of 2-Chloroethyl 1-Thio-β-D-glycopyranosides Derived from D-Galactose, D-Glucose, and 2-Acetamido-2-deoxy-D-glucose

  摘要：

  D-半乳糖 和D-葡萄糖 构型的氯乙基1-硫代-β-D-吡喃糖苷 5a-5c 通过用1-溴-2-氯乙烷烷基化相应的1-硫代-β-D-己糖吡喃糖 3a-3c，然后去乙酰化制备而成。起始的1-硫代-β-D-己糖吡喃糖是通过乙酰化的吡喃糖卤代物 经由 异硫脲盐获得的。实验证明，氯乙基硫代糖苷 5a-5c 在水溶液中发生水解，生成2-羟乙基硫代糖苷 6a-6c 和还原性己糖，并且这种水解是通过环硫銨盐进行的。水解过程通过 ¹H 和 ¹³C NMR光谱进行监测。在含酚或苯胺的1%碳酸钠水溶液中，硫代糖苷 5a-5c 除了产生上述水解产物外，还生成苯氧乙基和苯胺基乙基硫代糖苷 9a、10a和 9b、10b。

  DOI：

  10.1135/cccc19961489
• 作为产物：
  描述：

  β-D-葡萄糖五乙酸酯 在 Amberlyst A-26 F- resin 、 三氟化硼乙醚 作用下， 生成 2-bromoethyl 1-deoxy-1-thio-2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside
  参考文献：
  名称：

  通过碳水化合物S-（O，O-二烷基）磷酸二硫盐和单硫盐与氟阴离子的反应合成S-（1-和2-卤代烷基）糖的新颖实用方法

  摘要：

  已经开发了高产率和高纯度的S-（1-和2-卤代烷基）糖的有用的合成方法。易得的糖S-（O，O-二烷基）硫代二硫代磷酸酯在与氟离子反应后发生S-P键断裂，生成相应的糖硫醇酸酯，然后与二氯甲烷或1,2-二卤代烷烃在反应介质中进一步原位反应。在该反应中，卤代烷烃起反应物和溶剂的作用。

  DOI：

  10.1016/j.tetlet.2003.12.155

文献信息

• 2-Haloethyl 1-Thioglycosides as New Tools in Glycoside Syntheses. Part 1: Preparation, Characteristics, General Reactions
  作者：Andreas Krüger、Jutta Pyplo-Schnieders、Hartmut Redlich、Pär Winkelmann

  DOI：10.1135/cccc20041843

  日期：——

  2-Haloethyl 1-thioglycosides are excellent leaving groups when the 2-haloethyl function is activated with silver salts or Lewis acids. These thioglycosides can be synthesized on the original Černý route or for better compatibility with the needs of a more complex glycoside synthesis, in stepwise procedures via 2-(2-tetrahydropyran-2-yloxy)ethyl glycosides or trityl 1-thioglycosides. The initial step in glycosidation reaction presumably proceeds via a thiiranium ion, which is responsible for their increased reactivity compared with normal thioethers as leaving groups in glycoside syntheses. Basic features of this new system with respect to reactivity and selectivity in disaccharide syntheses are described.

  2-卤乙基1-硫代糖苷在2-卤乙基功能被银盐或Lewis酸激活时是优秀的离去基团。这些硫代糖苷可以在原始Černý路线上合成，或者为了更复杂的糖苷合成需求与之更兼容，在通过2-(2-四氢吡喃-2-氧基)乙基糖苷或三苯基1-硫代糖苷的逐步程序中合成。糖苷化反应的初始步骤可能通过硫代环氧离子进行，这对于它们在糖苷合成中作为离去基团的反应性增加具有责任。描述了这种新系统在二糖合成中的反应性和选择性的基本特征。
• Asymmetric sulfur atom coordination in a copper(ii) dipicolylamine (DPA) complex with a thioglycoside ligand
  作者：Yuko Sugai、Shoko Fujii、Tomomi Fujimoto、Shigenobu Yano、Yuji Mikata

  DOI：10.1039/b706423c

  日期：——

  The 2,2′-dipicolylamine (DPA)-tethered thioglycoside ligand, N,N-bis(2-pyridylmethyl)-2-aminoethyl 1-deoxy-1-thio-2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside (sL1), has been prepared and its copper(II) complex synthesized. Using copper(II) chloride, the copper complex was isolated as a chloride-bound species formulated as [Cu(sL1)Cl(ClO4)] (1). The corresponding O-glycoside complex ([Cu(L1)Cl](ClO4), 2) was also prepared using L1 (N,N-bis(2-pyridylmethyl)-2-aminoethyl 2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside), and both complexes were characterized and compared by means of X-ray crystallography, cyclic voltammetry, electronic absorption and circular dichroism (CD) spectra. Although both complexes exhibited similar copper coordination geometries, the absolute configuration of the O/S chiral center generated by the copper coordination was inverted. The electronic and CD spectra of acetonitrile solutions of 1 and 2 were different likely due to the presence of a copper–sulfur charge-transfer band for 1. Complex 1 also exhibits a large Cotton effect around 700 nm. The corresponding d–d transition of the copper(II) center reveals that the asymmetric copper–sulfur (oxygen) coordination remains even in solution.

  我们制备了 2,2′-二二甲胺（DPA）系硫糖苷配体 N,N-双（2-吡啶基甲基）-2-氨基乙基 1-脱氧-1-硫代-2,3,4,6-四-O-乙酰基-β-D-吡喃葡萄糖苷（sL1），并合成了其铜（II）络合物。利用氯化铜（II），分离出了与氯结合的铜络合物[Cu(sL1)Cl(ClO4)] (1)。我们还利用 L1（N,N-双（2-吡啶基甲基）-2-氨基乙基 2,3,4,6-四-O-乙酰基-β-D-吡喃葡萄糖苷）制备了相应的 O-糖苷配合物（[Cu(L1)Cl]( )，2），并通过 X 射线晶体学、循环伏安法、电子吸收和圆二色性（CD）光谱对这两种配合物进行了表征和比较。虽然这两种配合物表现出相似的铜配位几何结构，但铜配位产生的 O/S 手性中心的绝对构型是颠倒的。1 和 2 的乙腈溶液的电子和 CD 光谱不同，这可能是由于 1 存在铜硫电荷转移带。络合物 1 在 700 纳米波长附近也表现出很大的科顿效应。铜（II）中心的相应 d-d 转变表明，即使在溶液中，铜-硫（氧）的不对称配位仍然存在。
• Synthesis and Studies of Mononucleoside Glucosyl Phosphotriester Derivatives
  作者：Nathalie Schlienger、Christian Périgaud、Gilles Gosselin、Jean-Louis Imbach

  DOI：10.1021/jo9706638

  日期：1997.10.1

  The synthesis and stability studies in several aqueous media of mononucleoside glucosyl phosphotriester derivatives of 3'-azido-3'-deoxythymidine are reported herein, Such neutral mononucleotides, which incorporate beta-glucopyranosidyl moieties associated to a thioethyl Linker as phosphate protecting groups were designed to act as ''pronucleotides'', giving rise to the corresponding 5'-mononucleotide through a glucosidase-mediated activation mechanism.
• Cerny; Pacak, Collection of Czechoslovak Chemical Communications, 1959, vol. 24, p. 2566,2567
  作者：Cerny、Pacak

  DOI：——

  日期：——