phenyl 4,6-O-benzylidene-3-deoxy-3-C-methyl-3-nitro-1-thio-α-D-glucopyranoside | 302785-17-7

• 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: phenyl 4,6-O-benzylidene-3-deoxy-3-C-methyl-3-nitro-1-thio-α-D-glucopyranoside
• CAS: 302785-17-7
• 化学式: C₂₀H₂₁NO₆S
• 分子量: 403.456
• InChiKey: PLUJSMCUQZCCNY-DNDRQTMDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.01
• 重原子数：
  28.0
• 可旋转键数：
  4.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  91.06
• 氢给体数：
  1.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  phenyl 4,6-O-benzylidene-3-deoxy-3-C-methyl-3-nitro-1-thio-α-D-glucopyranoside 在 4,4'-二氨基二苯乙烯-2,2'-二磺酸 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以9.5%的产率得到2,5-anhydro-4,6-O-benzylidene-1,3-dideoxy-1-fluoro-3-C-methyl-3-nitro-1-phenylthio-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 、 phenyl 3-deoxy-3-C-methyl-3-nitro-1-thio-D-glucopyranoside 在 对甲苯磺酸 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 phenyl 4,6-O-benzylidene-3-deoxy-3-C-methyl-3-nitro-1-thio-β-D-glucopyranoside 、 phenyl 4,6-O-benzylidene-3-deoxy-3-C-methyl-3-nitro-1-thio-α-D-glucopyranoside
  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

文献信息

• 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.