methyl 5-thio-β-L-arabinopyranoside | 218906-61-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻烷
• 英文名称: methyl 5-thio-β-L-arabinopyranoside
• 英文别名: (2S,3R,4S,5R)-2-methoxythiane-3,4,5-triol
• CAS: 218906-61-7
• 化学式: C₆H₁₂O₄S
• 分子量: 180.225
• InChiKey: MUKTYNFJWVWKKD-AZGQCCRYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.2
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  95.2
• 氢给体数：
  3
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 5-thio-β-L-arabinopyranoside 在 咪唑 、 sodium tetrahydroborate 、 三氟甲磺酸三甲基硅酯 、 水 、 对甲苯磺酸 、 三乙胺 、 N,N-二异丙基乙胺 、 间氯过氧苯甲酸 作用下， 生成 4'-硫代尿苷
  参考文献：
  名称：

  白霉素核苷抗生素硫庚糖核中非典型立体化学的生物合成起源

  摘要：

  白霉素是肽基硫代核苷天然产物，对临床上重要的病原体显示出抗菌活性。它们的结构以具有非典型立体化学的硫庚糖为特征，包括用 d-氨基酸部分修饰的 d-呋喃木糖环。在本文中证明，AbmH 是一种依赖于 5'-磷酸 (PLP) 的吡哆醛转醛缩酶，其催化苏式选择性醛醇型反应以生成具有 d-呋喃核糖环和 l-氨基酸部分的硫庚糖核心。L-氨基酸构型向d-氨基酸构型的转化由PLP依赖性差向异构酶AbmD催化。根据基因缺失实验，硫代呋喃糖环从 d-核糖到 d-木糖的转化似乎是由 AbmJ 介导的，AbmJ 被注释为自由基 S-腺苷-l-甲硫氨酸 (SAM) 酶。

  DOI：

  10.1021/jacs.8b12565
• 作为产物：
  描述：

  L-阿拉伯糖 在 吡啶 、 盐酸 、 sodium methylate 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 生成 methyl 5-thio-β-L-arabinopyranoside
  参考文献：
  名称：

  实用的4'-硫代核糖核苷合成

  摘要：

  描述了从廉价的1-阿拉伯糖开始的4'-硫代核糖核苷的实际合成。通过使用新型的还原性环收缩反应制备的1,4-脱水-2,3 - O-异亚丙基-4-硫代核糖醇被转化为5-O-甲硅烷基化的亚砜。亚砜的Pummerer型硫糖基化立体选择性地产生了4'-硫代核糖核苷。

  DOI：

  10.1016/j.tetlet.2005.11.049

文献信息

• Synthesis and Properties of 4′-ThioLNA/BNA
  作者：Rion Maeda、Noriko Saito-Tarashima、Hideaki Wakamatsu、Yoshihiro Natori、Noriaki Minakawa、Yuichi Yoshimura

  DOI：10.1021/acs.orglett.1c01306

  日期：2021.5.21

  applicable to oligonucleotide therapeutics, we designed a 4′-thio analogue of an LNA/BNA monomer. Synthesis of 4′-hydroxymethyl-4′-thioribonucleoside was achieved by a tandem ring-contraction-aldol reaction of a 5-thiopyranose derivative and the subsequent Pummerer-type thioglycosylation reaction of the corresponding sulfoxide. Treatment of 4′-hydroxymethyl-4′-thiopyrimidine nucleosides with diphenyl

  为了开发适用于寡核苷酸治疗的新核苷类似物，我们设计了LNA / BNA单体的4'-硫代类似物。4'-羟甲基-4'-硫代核糖核苷的合成是通过5-硫代吡喃糖衍生物的串联环缩合-醛醇缩合反应和随后的相应亚砜的Pummerer型硫代糖基化反应实现的。在催化NaHCO 3存在下用碳酸二苯酯处理4'-羟甲基-4'-硫代嘧啶核苷，得到所需的4'-thioLNA / BNA单体，将其引入寡核苷酸中。
• Synthesis of 4-cyanophenyl and 4-nitrophenyl 1,5-dithio-l- and -d-arabinopyranosides possessing antithrombotic activity1Orally active antithrombotic thioglycosides, Part VI. For Part V, see[1].12Presented partly at the XVIIIth International Carbohydrate Symposium, Milan, 21–26 July 1996. Abstr. BP092.2
  作者：Éva Bozó、Sándor Boros、János Kuszmann

  DOI：10.1016/s0008-6215(98)00221-3

  日期：1998.10

  5-S-Benzoyl-2,3-O-isopropylidene-5-thio-L-arabinose, prepared from L-arabinose diethyl dithioacetal gave, on treatment with sodium methoxide in methanol, 4-O-benzoyl-2,3-O-isopropylidene-5-thio-L-arabinopyranose 12 which was converted into its 1-O-acetate 14. Hydrolysis of 12 in acetic acid-water afforded, after acetylation, 1,2,3-tri-O-acetyl-4-O-benzoyl-5-thio-L-ara-binopyranose 17 which was transformed into 2,3-di-O-acetyl-4-O-benzoyl-5-thio-L-arabinopyranosyl bromide 20. Zemplen deacylation of 17 gave 5-thio-L-arabinopyranose which was converted via 1,2,3,4-tetra-O-acetyl-5-thio-beta-L-arabinopyranose 5 into 2,3,4-tri-O-acetyl-5-thio-beta-L-arabinopyranosyl bromide 6 and into O-(2,3,4-tri-O-acetyl-5-thio-L-arabinopyranosyl) trichloro-acetimidate 7. Glycosidation of 4-nitrophenol with 12 under the Mitsunobu conditions afforded 4-nitrophenyl 4-O-benzoyl-2,3-O-isopropylidene-5-thio-alpha- and beta-L-arabinopyranoside in a similar to 1:2 ratio. Condensation of the glycosyl donors 6, 7, 17, and 20 with 4-cyano- and 4-nitrobenzenethiol yielded, after deacylation, 4-cyano- and 4-nitrophenyl 1,5-dithio-alpha- and beta-L-arabinopyranosides 28 alpha, 28 beta, 29 alpha and 29 beta in different ratios and yields, depending on the reaction conditions applied. In a similar manner the corresponding D-isomers 30 alpha, 30 beta, 31 alpha and 31 beta were also prepared. All of these glycosides, except 28 alpha, showed a stronger oral antithrombotic effect in rats as compared to beciparcil, used as reference. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Biosynthetic Origin of the Atypical Stereochemistry in the Thioheptose Core of Albomycin Nucleoside Antibiotics
  作者：Richiro Ushimaru、Hung-wen Liu

  DOI：10.1021/jacs.8b12565

  日期：2019.2.13

  d-ribofuranose ring and an l-amino acid moiety. The conversion of l-to d-amino acid configuration is catalyzed by the PLP-dependent epimerase AbmD. The d- ribo to d- xylo conversion of the thiofuranose ring appears according to gene deletion experiments to be mediated by AbmJ, which is annotated as a radical S-adenosyl-l-methionine (SAM) enzyme. These studies establish several key steps in the assembly of the

  白霉素是肽基硫代核苷天然产物，对临床上重要的病原体显示出抗菌活性。它们的结构以具有非典型立体化学的硫庚糖为特征，包括用 d-氨基酸部分修饰的 d-呋喃木糖环。在本文中证明，AbmH 是一种依赖于 5'-磷酸 (PLP) 的吡哆醛转醛缩酶，其催化苏式选择性醛醇型反应以生成具有 d-呋喃核糖环和 l-氨基酸部分的硫庚糖核心。L-氨基酸构型向d-氨基酸构型的转化由PLP依赖性差向异构酶AbmD催化。根据基因缺失实验，硫代呋喃糖环从 d-核糖到 d-木糖的转化似乎是由 AbmJ 介导的，AbmJ 被注释为自由基 S-腺苷-l-甲硫氨酸 (SAM) 酶。
• A practical synthesis of 4′-thioribonucleosides
  作者：Yuichi Yoshimura、Tetsuya Kuze、Mari Ueno、Fumiko Komiya、Kazuhiro Haraguchi、Hiromichi Tanaka、Fumitaka Kano、Kohei Yamada、Kazuhiro Asami、Nobuaki Kaneko、Hiroki Takahata

  DOI：10.1016/j.tetlet.2005.11.049

  日期：2006.1

  A practical synthesis of 4′-thioribonucleosides starting from inexpensive l-arabinose is described. 1,4-Anhydro-2,3-O-isopropylidene-4-thioribitol, which was prepared by using a novel reductive ring-contraction reaction, was converted to the 5-O-silylated sulfoxides. The Pummerer-type thioglycosylation of the sulfoxides gave the 4′-thioribonucleosides stereoselectively.

  描述了从廉价的1-阿拉伯糖开始的4'-硫代核糖核苷的实际合成。通过使用新型的还原性环收缩反应制备的1,4-脱水-2,3 - O-异亚丙基-4-硫代核糖醇被转化为5-O-甲硅烷基化的亚砜。亚砜的Pummerer型硫糖基化立体选择性地产生了4'-硫代核糖核苷。