(2R,3S,4S)-5-fluoro-2-(hydroxymethyl)-3,4-dihydro-2H-pyran-3,4-diol | 187088-14-8

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 卤代醇
• 英文名称: (2R,3S,4S)-5-fluoro-2-(hydroxymethyl)-3,4-dihydro-2H-pyran-3,4-diol
• CAS: 187088-14-8
• 化学式: C₆H₉FO₄
• 分子量: 164.133
• InChiKey: AOICZLXDBBWICL-HSUXUTPPSA-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：
  0.67
• 拓扑面积：
  69.9
• 氢给体数：
  3
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2R,3S,4S)-5-fluoro-2-(hydroxymethyl)-3,4-dihydro-2H-pyran-3,4-diol 、 碘甲烷 在 sodium hydroxide 、 二甲基亚砜 作用下， 以69%的产率得到(2R,3R,4S)-5-Fluoro-3,4-dimethoxy-2-methoxymethyl-3,4-dihydro-2H-pyran
  参考文献：
  名称：

  A synthesis of 2-fluoroglucal derivatives

  摘要：

  3,4,6-Tri-O-methyl-D-glucal, readily prepared from 3,4,6-tri-O-acetyl-D-glucal, undergoes lithiation at -78 degrees C in THF with t-BuLi to afford a vinyl carbanion, which can be trapped with electrophiles in moderate overall yields. The palladium coupling and Dotz-type reactions of these intermediates are also described. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2006.08.122
• 作为产物：
  描述：

  3,4,6-tri-O-acetyl-2-deoxy-2-fluoro-α-D-glucopyranosyl bromide 在 sodium 、 三乙胺 作用下， 以 甲醇 、 乙腈 为溶剂， 生成 (2R,3S,4S)-5-fluoro-2-(hydroxymethyl)-3,4-dihydro-2H-pyran-3,4-diol
  参考文献：
  名称：

  A synthesis of 2-fluoroglucal derivatives

  摘要：

  3,4,6-Tri-O-methyl-D-glucal, readily prepared from 3,4,6-tri-O-acetyl-D-glucal, undergoes lithiation at -78 degrees C in THF with t-BuLi to afford a vinyl carbanion, which can be trapped with electrophiles in moderate overall yields. The palladium coupling and Dotz-type reactions of these intermediates are also described. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2006.08.122

文献信息

• Substituted glycals as probes of glycosidase mechanisms
  作者：Ellen C.K. Lai、Sandra A. Morris、Ian P. Street、Stephen G. Withers

  DOI：10.1016/s0968-0896(96)00175-7

  日期：1996.11

  D-Glucal and a series of substituted derivatives have been tested as substrates, inhibitors and inactivators of the Agrobacterium faecalis beta-glucosidase in order to probe structure/function relationships in this enzyme. D-Glucal is shown to be a substrate (k(cat)=2.3 min(-1), K-m=0.85 mM) undergoing hydration with stereospecific protonation from the alpha-face to yield 2-deoxy-beta-D-glucose. 1-Methyl-D-glucal surprisingly serves as only a poor substrate (k(cat)=0.056 min(-1), K-m=57 mM), also undergoing protonation from the alpha-face. 2-Fluoro-D-glucal, however, is completely inert, as a result of inductive destabilisation of the oxocarbenium ion-like transition state for protonation, and functions only as a relatively weak (K-i = 24 mM) inhibitor. Similar behaviour was seen with almond beta-glucosidase and yeast alpha-glucosidase and for the interaction of 2-fluoro-D-galactal with Escherichia coli beta-galactosidase. A series of of alpha,beta-unsaturated glucal derivatives was also synthesised and tested as potential substrates, inhibitors or inactivators of A. faecalis beta-glucosidase. Of these only 1-nitro-D-glucal functioned as a time dependent, irreversible inactivator (k(i)=0.011 min(-1), K-i=5.5 mM), presumably acting as a Michael acceptor. Electrospray mass spectrometric analysis revealed mutliple labeling of the enzyme by this inactivator, lessening its usefulness as an affinity label. Less reactive Michael acceptor glycals which might have been more specific (1-cyano-, 2-cyano-, 1-carboxylic acid, 1-carboxylic acid methyl ester) unfortunately did not function as inactivators or substrates, only as relatively weak reversible inhibitors (K-i=3-96 mM). Copyright (C) 1996 Elsevier Science Ltd
• A synthesis of 2-fluoroglucal derivatives
  作者：Ewan Boyd、Ray V.H. Jones、Peter Quayle、Anita J. Waring (née Potts)

  DOI：10.1016/j.tetlet.2006.08.122

  日期：2006.11

  3,4,6-Tri-O-methyl-D-glucal, readily prepared from 3,4,6-tri-O-acetyl-D-glucal, undergoes lithiation at -78 degrees C in THF with t-BuLi to afford a vinyl carbanion, which can be trapped with electrophiles in moderate overall yields. The palladium coupling and Dotz-type reactions of these intermediates are also described. (c) 2006 Elsevier Ltd. All rights reserved.