3-O-benzyl-1,2-O-isopropylidene-5-O-trifluoromethanesulfonyl-α-D-ribofuranoside | 151075-97-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3-O-benzyl-1,2-O-isopropylidene-5-O-trifluoromethanesulfonyl-α-D-ribofuranoside
• 英文别名: [(3aR,5R,6R,6aR)-2,2-dimethyl-6-phenylmethoxy-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-5-yl]methyl trifluoromethanesulfonate
• CAS: 151075-97-7
• 化学式: C₁₆H₁₉F₃O₇S
• 分子量: 412.384
• InChiKey: IOHIFFLNVDAVIK-AAVRWANBSA-N

物化性质

• 沸点：
  431.8±45.0 °C(predicted)
• 密度：
  1.44±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  27
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  88.7
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  3-O-benzyl-1,2-O-isopropylidene-5-O-trifluoromethanesulfonyl-α-D-ribofuranoside 在 六甲基磷酰三胺 、 lithium diisopropyl amide 作用下， 反应 0.4h， 生成 3-((3aR,5R,6R,6aR)-6-Benzyloxy-2,2-dimethyl-tetrahydro-furo[2,3-d][1,3]dioxol-5-yl)-2-((3aR,5R,6R,6aR)-6-benzyloxy-2,2-dimethyl-tetrahydro-furo[2,3-d][1,3]dioxol-5-ylmethyl)-propionitrile
  参考文献：
  名称：

  用 C-亲核试剂取代三氟甲磺酸糖：D-吡喃葡萄糖和 D-呋喃核糖链延伸和功能化

  摘要：

  摘要 甲基 4-O-苄基-2,3-二-O-甲氧基甲基-6-O-1-6-O-三氟甲磺酰基-α-D-吡喃葡萄糖苷 1 或 3-O-苄基-1,2-O 的处理-isopropylidene-5-O-trifluoromethenesulfonyl-α-D-ribofuranoside 2 在 THF/HMPA 中与各种官能化的 C-亲核试剂一起产生相应的链延长糖，产率非常好。

  DOI：

  10.1080/00397919408010152
• 作为产物：
  描述：

  1,2-O-isopropylidene-3-O-benzyl-5-O-tert-butyldiphenylsilyl-α-D-ribofuranose 在 吡啶 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 1.5h， 生成 3-O-benzyl-1,2-O-isopropylidene-5-O-trifluoromethanesulfonyl-α-D-ribofuranoside
  参考文献：
  名称：

  Study of 1-Deoxy-d-xylulose-5-phosphate Reductoisomerase:  Synthesis and Evaluation of Fluorinated Substrate Analogues

  摘要：

  1-Deoxy-D-xylulose-5-phosphate (DXP) reductoisomerase is a NADPH-dependent enzyme catalyzing the conversion of DXP to methyl-D-erythritol 4-phosphate (MEP). In this study, each of the hydroxyl groups in DXP and one of its C-1 hydrogen atoms, were separately replaced with a fluorine atom and the effect of the substitution on the catalytic turnover was examined. It was found that the 1-fluoro-DXP is a poor substrate, while both 3- and 4-fluoro-DXP behave as noncompetitive inhibitors.

  DOI：

  10.1021/ol048459b

文献信息

• Diallyl (Lithiodifluoromethyl)phosphonate: A New Reagent for the Introduction of the (Difluoromethylene)phosphonate Functionality
  作者：David B. Berkowitz、Darby G. Sloss

  DOI：10.1021/jo00126a073

  日期：1995.10
• Synthesis of (.alpha.,.alpha.-difluoroalkyl)phosphonates by displacement of primary triflates
  作者：David B. Berkowitz、MariJean Eggen、Quanrong Shen、Darby G. Sloss

  DOI：10.1021/jo00075a005

  日期：1993.11

  Simple primary alkyl triflates and those derived from several monosaccharides are cleanly displaced by diethyl (lithiodifluoromethyl)phosphonate to provide the corresponding (alpha,alpha-difluoroalkyl)phosphonates in minutes at -78-degrees-C.
• Facile installation of the phosphonate and (α,α-difluoromethyl)phosphonate functionalities equipped with benzyl protection
  作者：David B. Berkowitz、Debnath Bhuniya、Gorka Peris

  DOI：10.1016/s0040-4039(99)00077-5

  日期：1999.3

  Under appropriate conditions, dibenzyl (lithiomethyl)phosphonate and dibenzyl (lithiodifluoromethyl)phosphonate displace primary triflates to provide convenient access to the corresponding phosphonates, carrying benzyl ester protecting groups. This approach is of particular advantage for phosphonate ester deprotection, which may be achieved by simple hydrogenolysis. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Synthesis of 5'-Deoxy-5'-Difluoromethyl Phosphonate Nucleotide Analogs
  作者：Jasenka Matulic-Adamic、Peter Haeberli、Nassim Usman

  DOI：10.1021/jo00113a040

  日期：1995.4

  synthetic route to nucleoside 5'-deoxy-5'-difluoromethyl phosphonates from ribofuranosyl 5-deoxy-5-difluoromethyl phosphonate precursors is described. Methyl 5,6-dideoxy-6-(diethoxyphosphinyl)-6.6-difluoro-2,3-O-isopropylidene-beta-D-ribo-hexofuranoside (7) was converted, under mild conditions, to the suitable glycosylating agent 1-O-acetyl-2,3-di-O-benzoyl-5,6-dideoxy-6,6-difluoro-beta-D-ribo-hexofuranoside (10). 1,2-Di-O-acetyl-3-O-benzyl-5,6-dideoxy-6-(diethoxyphosphinyl)-6,6-difluoro-P-D-ribo-hexofuranoside (16) was also prepared as a versatile building block for nucleotide synthesis. Condensation of 10 with silylated nucleobases, followed by complete deprotection, afforded 5',6'-dideoxy-6'-(dihydroxyphosphinyl)-6'6'-difluoro nucleoside analogs 22a-c. In the case of the glycosylation of adenine, a considerable quantity of N-7 regioisomer 19 was formed. 5',6'-Dideoxy-6'-(dihydroxyphosphinyl)-6 adenosine analog 22e was converted into the triphosphate analog 23 using 1,1'-carbonyldiimidazole activation followed by condensation with pyrophosphate. The adenosine 3',5-cyclic monophosphate analog 24 was obtained through the DCC promoted intramolecular cyclization of 22c. Dinucleoside phosphate analog 27 was prepared by DCC-catalyzed coupling of 1-[2,3-di-O-benzoyl-5,6-dideoxy-6-(dihydroxyphosphinyl)-6,6-difluoro-P-D-ribo-hexofuranosyl]uracil (21a) with 2',5'-bis(O-tert-butyldimethylsilyl)-N-4-cytidine (25), followed by deprotection.
• A Convergent Triflate Displacement Approach to (α-Monofluoroalkyl)phosphonates
  作者：David B. Berkowitz、Mohua Bose、Nathan G. Asher

  DOI：10.1021/ol015983z

  日期：2001.6.1

  Treatment of primary alkyl triflates or iodides with the potassium salt of diethyl (alpha -fluoro-alpha -phenylsulfonyl methyl)phosphonate yields (alpha -fluoro-alpha -phenylsulfonylalkyl)phosphonate These can be cleanly desulfonated, in a matter of minutes, with Na(HS) in MeOH/THF/NaH2PO4. This two-step procedure complements previously reported triflate displacement approaches to alpha -nonfluorinated and alpha,alpha -difluorinated phosphonates.