2,5-anhydro-3,6-di-O-benzyl-4-deoxy-4-fluoro-aldehydo-D-talose | 676265-76-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,5-anhydro-3,6-di-O-benzyl-4-deoxy-4-fluoro-aldehydo-D-talose
• 英文别名: (2S,3R,4S,5R)-4-fluoro-3-phenylmethoxy-5-(phenylmethoxymethyl)oxolane-2-carbaldehyde
• CAS: 676265-76-2
• 化学式: C₂₀H₂₁FO₄
• 分子量: 344.383
• InChiKey: CXBXWYXKHRGWBH-YSTOQKLRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  25
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  tert-butyl (3aR,4R,6aS)-4-(aminomethyl)tetrahydro-2,2-dimethyl-5H-[1,3]dioxolo[4,5-c]pyrrole-5-carboxylate 、 2,5-anhydro-3,6-di-O-benzyl-4-deoxy-4-fluoro-aldehydo-D-talose 在 三乙酰氧基硼氢化钠 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 1.5h， 生成 (3aR,4R,6aS)-4-{[((2R,3R,4S,5R)-3-Benzyloxy-5-benzyloxymethyl-4-fluoro-tetrahydro-furan-2-ylmethyl)-amino]-methyl}-2,2-dimethyl-tetrahydro-[1,3]dioxolo[4,5-c]pyrrole-5-carboxylic acid tert-butyl ester
  参考文献：
  名称：

  一种合成 N-取代 1-C-氨基甲基呋喃糖苷的新方法

  摘要：

  甲酰基 C-呋喃糖苷的还原胺化，很容易通过 DAST 促进的环收缩从己糖衍生的赤道-2-OH-吡喃糖苷中获得，在大多数情况下以高产率提供 N-取代的 1-C-氨基甲基呋喃糖苷。

  DOI：

  10.1055/s-2005-922762
• 作为产物：
  描述：

  methyl 4,6-O-benzylidene-3-O-benzyl-α-D-glucopyranoside 在 二乙胺基三氟化硫 、 3 A molecular sieve 、 sodium cyanoborohydride 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 3.0h， 生成 2,5-anhydro-3,6-di-O-benzyl-4-deoxy-4-fluoro-aldehydo-D-talose
  参考文献：
  名称：

  Fluorination of 2-hydroxy-hexopyranosides by DAST: towards formyl C-glycofuranosides from equatorial-2-OH methyl hexopyranosides

  摘要：

  Reaction of diversely configured and substituted, unbranched methyl D-hexopyranosides with the DAST in dichloromethane or acetonitrile led to normal substitution products and/or rearranged fluoro compounds (ring-contracted 2,5-anhydro-1-fluoro-1-I-methylhexitol derivatives, 2-methoxy-D-hexopyranosyl fluorides, and, for some 3-azido substrates, rearranged 2-azido-3-fluoro-D-hexopyranosides). When the reaction was performed in acetonitrile, the solvent participation as a nucleophile (Ritter reaction) was observed in one case. For a 2,4-unprotected 3-azido substrate, 2,3-dehydration and fluorination at C(4), the latter with epimerization, took place. F-19/H-1 and F-19/C-13 coupling constant values were systematically applied to discriminate between isomeric structures for fluorinated products, and for some, previously described, coming from five 3-branched-chain D- or L-hexopyranosides, thus discarding the previously reported structural assignment. From the synthetic point of view, the most outstanding result was the preparation of 2,5-anhydro-1-fluoro-1-O-methylhexitols, showing a latent formyl group functionality, a transformation, which was achieved in one case. A rationalization for the formation of the different types of product is also proposed. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2003.11.034

文献信息

• A Novel Approach to the Synthesis of N-Substituted 1-<i>C</i>-Aminomethyl Glycofuranosides
  作者：Francisca Cabrera-Escribano、Yolanda Vera-Ayoso、Pastora Borrachero、Manuel Gómez-Guillén、Pierre Vogel

  DOI：10.1055/s-2005-922762

  日期：——

  Reductive amination of formyl C-glycofuranosides, easily available from hexose-derived equatorial-2-OH-glycopyranosides by DAST-promoted ring contraction, afforded N-substituted 1-C-aminomethyl glycofuranosides in most cases in high yields.

  甲酰基 C-呋喃糖苷的还原胺化，很容易通过 DAST 促进的环收缩从己糖衍生的赤道-2-OH-吡喃糖苷中获得，在大多数情况下以高产率提供 N-取代的 1-C-氨基甲基呋喃糖苷。
• Fluorination of 2-hydroxy-hexopyranosides by DAST: towards formyl C-glycofuranosides from equatorial-2-OH methyl hexopyranosides
  作者：Yolanda Vera-Ayoso、Pastora Borrachero、Francisca Cabrera-Escribano、Ana T. Carmona、Manuel Gómez-Guillén

  DOI：10.1016/j.tetasy.2003.11.034

  日期：2004.2

  Reaction of diversely configured and substituted, unbranched methyl D-hexopyranosides with the DAST in dichloromethane or acetonitrile led to normal substitution products and/or rearranged fluoro compounds (ring-contracted 2,5-anhydro-1-fluoro-1-I-methylhexitol derivatives, 2-methoxy-D-hexopyranosyl fluorides, and, for some 3-azido substrates, rearranged 2-azido-3-fluoro-D-hexopyranosides). When the reaction was performed in acetonitrile, the solvent participation as a nucleophile (Ritter reaction) was observed in one case. For a 2,4-unprotected 3-azido substrate, 2,3-dehydration and fluorination at C(4), the latter with epimerization, took place. F-19/H-1 and F-19/C-13 coupling constant values were systematically applied to discriminate between isomeric structures for fluorinated products, and for some, previously described, coming from five 3-branched-chain D- or L-hexopyranosides, thus discarding the previously reported structural assignment. From the synthetic point of view, the most outstanding result was the preparation of 2,5-anhydro-1-fluoro-1-O-methylhexitols, showing a latent formyl group functionality, a transformation, which was achieved in one case. A rationalization for the formation of the different types of product is also proposed. (C) 2003 Elsevier Ltd. All rights reserved.