3,4,6-tri-O-acetyl-2-fluoro-D-galactal | 628705-64-6

• 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: 3,4,6-tri-O-acetyl-2-fluoro-D-galactal
• 英文别名: [(2R,3S,4S)-3,4-diacetyloxy-5-fluoro-3,4-dihydro-2H-pyran-2-yl]methyl acetate
• CAS: 628705-64-6
• 化学式: C₁₂H₁₅FO₇
• 分子量: 290.245
• InChiKey: NDCAFYPFDMYCNS-UTUOFQBUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  20
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  88.1
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  3,4,6-tri-O-acetyl-2-fluoro-D-galactal 在 N-氯代丁二酰亚胺 、 水 作用下， 以 四氢呋喃 为溶剂， 以70%的产率得到C₁₂H₁₆ClFO₈
  参考文献：
  名称：

  碳水化合物异头烷氧基的断裂：手性1-氟-1-卤-1-碘代糖醇的新合成。

  摘要：

  描述了一种新的通用方法，该方法可以从1,5-脱水-2-脱氧-己-1-烯醇衍生物（糖类）开始合成1,1,1-三卤代糖醇。在该方法的三个不同步骤中的每个步骤中依次引入卤素。在第一步中，通过起始糖基的亲电氟化引入氟。接下来，所得乙烯基氟化物的羟基卤代反应可随意添加任何卤素（F，Cl，Br或I），最后，通过烷氧基自由基裂解反应将碘原子插入。这种方法可以在温和的条件下制备与1,1,1-三卤代化合物（R--CF（2）I，R--CFI（2），R--CFClI和R--CFBrI）不同类型的化合物敏感的取代基。在某些情况下，R-CFClI和R-CFBrI生成的非对映异构体混合物可以进行色谱分离，并通过X射线晶体学分析确定其构型。这些化合物的合成有用性已通过检查C-1键断裂产生的氟化自由基的反应性进行了初步评估。

  DOI：

  10.1002/chem.200800734
• 作为产物：
  描述：

  3,4,6-tri-O-acetyl-2-deoxy-2-fluoro-α-D-galactopyranosyl bromide 在 三乙胺 作用下， 以 乙腈 为溶剂， 反应 18.0h， 生成 3,4,6-tri-O-acetyl-2-fluoro-D-galactal
  参考文献：
  名称：

  Syntheses of 2-deoxy-2-fluoro mono- and oligo-saccharide glycosides from glycals and evaluation as glycosidase inhibitors

  摘要：

  Several fluorinated oligosaccharides, including 2-deoxy-2-fluoro derivatives of cellobiose, maltose, and maltotriose were synthesized by the action of fluorine or acetyl hypofluorite on the corresponding glycal peracetates. Temperature effects on the stereoselectivities of these reactions were examined. Addition of acetyl hypofluorite to several 2-substituted glycals in the gluco or galacto series gave 2,2-disubstituted arabino- or lyxo-hexose derivatives; 3,4,6-tri-O-acetyl-2-fluoro-D-glucal or the analogous galactal yielded 2-deoxy-2,2-difluoro arabino- or lyxo-hexose peracetates, whereas 2-acetoxy-3,4,6-tri-O-acetyl-D-glucal or the analogous galactal gave 2(R)-2-acetoxy-2-fluoro-arabino- or lyxo-hexose peracetates, respectively. 2-Acetamido-3,4,6-tri-O-acetyl-D-glucal gave 2(R)-2-acetamido-2-acetoxy-3,4,6-tri-O-acetyl-alpha-D-arabino-hexopyranosyl fluoride. 2,4-Dinitrophenyl 2-deoxy-2-fluoro-beta-cellobioside was an inactivator of the exoglucanase from Cellulomonas fimi while 2-deoxy-2-fluoro-alpha-maltosyl and alpha-maltotriosyl fluorides were slow substrates of human pancreatic alpha-amylase and rabbit muscle glycogen debranching enzyme, respectively.

  DOI：

  10.1016/0008-6215(93)84061-a

文献信息

• Fragmentation of Carbohydrate Anomeric Alkoxyl Radicals:  A New Synthesis of 1,1-Difluoro-1-iodo Alditols
  作者：Cosme G. Francisco、Concepción C. González、Nieves R. Paz、Ernesto Suárez

  DOI：10.1021/ol035611l

  日期：2003.10.1

  [reaction: see text]. The beta-fragmentation of 2,2-difluoro-saccharide anomeric alkoxyl radicals, generated under oxidative condition by treatment of the respective alcohols with (diacetoxyiodo)benzene (DIB) and iodine, afforded 1,1-difluoro-1-iodo alditols in high yield. The reactivity of the fluorinated radical generated by rupture of the C-I bond has been preliminarily assessed by reductive deiodination

  [反应：请参见文字]。通过用（二乙酰氧基碘）苯（DIB）和碘处理相应的醇在氧化条件下产生的2,2-二氟糖异头烷氧基自由基进行β片段化反应，可得到高浓度的1,1-二氟-1-碘醛糖醇屈服。通过用氢化三丁基锡/ AIBN进行还原性碘化和使用Keck反应进行分子间烯丙基化，初步评估了CI键断裂所产生的氟化自由基的反应性。
• 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