methyl 4,6-O-benzylidene-3-deoxy-3-C-methyl-3-nitro-α-D-glucopyranoside | 237055-28-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: methyl 4,6-O-benzylidene-3-deoxy-3-C-methyl-3-nitro-α-D-glucopyranoside
• 英文别名: (2R,4aR,6S,7R,8R,8aS)-6-methoxy-8-methyl-8-nitro-2-phenyl-4a,6,7,8a-tetrahydro-4H-pyrano[3,2-d][1,3]dioxin-7-ol
• CAS: 237055-28-6
• 化学式: C₁₅H₁₉NO₇
• 分子量: 325.318
• InChiKey: GICUUUPGEGMFHN-ZAQNNHEOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  103
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl 4,6-O-benzylidene-3-deoxy-3-C-methyl-3-nitro-α-D-glucopyranoside 在 4,4'-二氨基二苯乙烯-2,2'-二磺酸 作用下， 以 二乙二醇二甲醚 为溶剂， 反应 16.0h， 以23%的产率得到2,5-anhydro-4,6-O-benzylidene-3-deoxy-1-fluoro-3-C-methyl-3-nitro-D-mannitol
  参考文献：
  名称：

  Rearrangement reactions in the fluorination of 3-deoxy-3-C-methyl-3-nitro-hexopyranosides (and hexo-1-thiopyranosides) of the d- and l-series by the DAST reagent

  摘要：

  Fluorination of diverse 3-deoxy-3-C-methyl-3-nitro-hexopyranosides and hexo-1-thiopyranosides of the D- and L-series by the DAST reagent was studied in order to establish, on this 3-branched-chain sugar domain, the influence of the stereochemical relationship of the substituents at positions 1 and 2, as well as the protection of the HO-4, on the kinds of rearrangement reaction promoted by this fluorinating agent. Three classes of pyranosidic substrate were employed. (a) 1,2-trans configured, irrespective of whether HO-4 is protected or not: (b) 4-O-protected 1,2-cis configured; and (c) 4-O-unprotected 1,2-cis configured. They were prepared starting from simple glycosides through routes involving a Baer reaction and subsequent transformations by known methodology. All the substrates of class a essayed underwent, on treatment with DAST at room or higher temperatures, a rearrangement involving a 1,2-shift to give both the anomeric 2-inverted pyranosyl fluorides (or, for the l-thioglycosides, only the a fluoride). Substrates of class b led, through a mechanism similar to that proposed for transformations of related substrates, to ring-contracted 2,5-anhydro-1-fluoro-1-O-methyl- (or 1-deoxy-1-phenylthio-)hexitol derivatives (sometimes as 1-epimers), which are precursors of 2,5-anhydro-aldehydo-sugars. Substrates of class c led to 4,5-anhydro-1-fluoro-1-O-methylalditol derivatives in all cases, together with a ring-contracted 5-fluoro-hexofuranoside ill only one case; a rationalisation for their formation is proposed. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(00)00252-4
• 作为产物：
  描述：

  苯甲醛二甲缩醛 、 methyl 3-deoxy-3-C-methyl-3-nitro-α-D-glucopyranoside methyl 3-deoxy-3-C-methyl-3-nitro-β-L-glucopyranoside 在 对甲苯磺酸 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 8.0h， 以42%的产率得到methyl 4,6-O-benzylidene-3-deoxy-3-C-methyl-3-nitro-α-D-glucopyranoside
  参考文献：
  名称：

  Branched-chain fluoro nitro d- and l-sugars from glucose

  摘要：

  sMixed crystals of methyl 3-deoxy-3-C-methyl-3-nitro-alpha-D- and beta-L-glucopyranosides (1:1), easily available from D-glucose by means of the Baer reaction, were completely characterised by X-ray diffraction analysis. These diastereomeric components, separation of which could be achieved through their 4,6-O-benzylidene derivatives, were selectively fluorinated at position 6 by treatment with DAST and stereoselectively transformed into phenyl 3-deoxy-3-C-methyl-3-nitro-1-thio-beta-D-glucopyranoside and phenyl 3-deoxy-3-C-methyl-3-nitro-1-thio-beta-L-glucopyranoside, respectively. Fluorination with DAST of each pure enantiomer afforded, depending on the conditions, the corresponding enantiomeric phenyl 3,6-dideoxy-6-fluoro-3-C-methyl-3-nitro-1-thio-beta-D- and beta-L-glucopyranosides or the respective rearranged 2,3,6-trideoxy-6-fluoro-3-C-methyl-3-nitro-2-alpha-D- and alpha-L-mannopyranosyl fluorides. This route constitutes a simple method for obtaining fair-to-good yields of 6-fluorinated branched-chain D- and L-sugar derivatives, potentially useful as glycosyl donors, starting from D-glucose. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(99)00156-1

文献信息

• Branched-chain fluoro nitro d- and l-sugars from glucose
  作者：Ana T Carmona、Pastora Borrachero、Francisca Cabrera-Escribano、Mª Jesús Diánez、Mª Dolores Estrada、Amparo López-Castro、Rafael Ojeda、Manuel Gómez-Guillén、Simeón Pérez-Garrido

  DOI：10.1016/s0957-4166(99)00156-1

  日期：1999.5

  sMixed crystals of methyl 3-deoxy-3-C-methyl-3-nitro-alpha-D- and beta-L-glucopyranosides (1:1), easily available from D-glucose by means of the Baer reaction, were completely characterised by X-ray diffraction analysis. These diastereomeric components, separation of which could be achieved through their 4,6-O-benzylidene derivatives, were selectively fluorinated at position 6 by treatment with DAST and stereoselectively transformed into phenyl 3-deoxy-3-C-methyl-3-nitro-1-thio-beta-D-glucopyranoside and phenyl 3-deoxy-3-C-methyl-3-nitro-1-thio-beta-L-glucopyranoside, respectively. Fluorination with DAST of each pure enantiomer afforded, depending on the conditions, the corresponding enantiomeric phenyl 3,6-dideoxy-6-fluoro-3-C-methyl-3-nitro-1-thio-beta-D- and beta-L-glucopyranosides or the respective rearranged 2,3,6-trideoxy-6-fluoro-3-C-methyl-3-nitro-2-alpha-D- and alpha-L-mannopyranosyl fluorides. This route constitutes a simple method for obtaining fair-to-good yields of 6-fluorinated branched-chain D- and L-sugar derivatives, potentially useful as glycosyl donors, starting from D-glucose. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Rearrangement reactions in the fluorination of 3-deoxy-3-C-methyl-3-nitro-hexopyranosides (and hexo-1-thiopyranosides) of the d- and l-series by the DAST reagent
  作者：Pastora Borrachero、Francisca Cabrera-Escribano、Ana T Carmona、Manuel Gómez-Guillén

  DOI：10.1016/s0957-4166(00)00252-4

  日期：2000.7

  Fluorination of diverse 3-deoxy-3-C-methyl-3-nitro-hexopyranosides and hexo-1-thiopyranosides of the D- and L-series by the DAST reagent was studied in order to establish, on this 3-branched-chain sugar domain, the influence of the stereochemical relationship of the substituents at positions 1 and 2, as well as the protection of the HO-4, on the kinds of rearrangement reaction promoted by this fluorinating agent. Three classes of pyranosidic substrate were employed. (a) 1,2-trans configured, irrespective of whether HO-4 is protected or not: (b) 4-O-protected 1,2-cis configured; and (c) 4-O-unprotected 1,2-cis configured. They were prepared starting from simple glycosides through routes involving a Baer reaction and subsequent transformations by known methodology. All the substrates of class a essayed underwent, on treatment with DAST at room or higher temperatures, a rearrangement involving a 1,2-shift to give both the anomeric 2-inverted pyranosyl fluorides (or, for the l-thioglycosides, only the a fluoride). Substrates of class b led, through a mechanism similar to that proposed for transformations of related substrates, to ring-contracted 2,5-anhydro-1-fluoro-1-O-methyl- (or 1-deoxy-1-phenylthio-)hexitol derivatives (sometimes as 1-epimers), which are precursors of 2,5-anhydro-aldehydo-sugars. Substrates of class c led to 4,5-anhydro-1-fluoro-1-O-methylalditol derivatives in all cases, together with a ring-contracted 5-fluoro-hexofuranoside ill only one case; a rationalisation for their formation is proposed. (C) 2000 Elsevier Science Ltd. All rights reserved.